Ronald W. Thring

Oil recovery from refinery oily sludge via ultrasound and freeze/thaw

The effective disposal of oily sludge generated from the petroleum industry has received increasing concerns, and oil recovery from such waste was considered as one feasible option. In this study, three different approaches for oil recovery were investigated, including ultrasonic treatment alone, freeze/thaw alone and combined ultrasonic and freeze/thaw treatment. The results revealed that the combined process could achieve satisfactory performance by considering the oil recovery rate and the total petroleum hydrocarbon (TPH) concentrations in the recovered oil and wastewater. The individual impacts of five different factors on the combined process were further examined, including ultrasonic power, ultrasonic treatment duration, sludge/water ratio in the slurry, as well as bio-surfactant (rhamnolipids) and salt (NaCl) concentrations. An oil recovery rate of up to 80.0% was observed with an ultrasonic power of 66 W and an ultrasonic treatment duration of 10 min when the sludge/water ratio was 1:2 without the addition of bio-surfactant and salt. The examination of individual factors revealed that the addition of low concentration of rhamnolipids (<100mg/L) and salt (<1%) to the sludge could help improve the oil recovery from the combined treatment process. The experimental results also indicated that ultrasound and freeze/thaw could promote the efficiency of each other, and the main mechanism of oil recovery enhancement using ultrasound was through enhanced desorption of petroleum hydrocarbons (PHCs) from solid particles.

Organic acid-induced release of lead from pyromorphite and its relevance to reclamation of Pb-contaminated soils.

The long-term stability of pyromorphite [Pb(5)(PO(4))(3)Cl] (PY) in root-soil interface (or rhizosphere) where production of organic acids from biological activities takes place is not fully understood. We conducted a 1-year long laboratory batch dissolution experiment to elucidate the release of Pb (and P) from PY by four commonly occurring low molecular weight organic acids (LMWOA) in rhizosphere: acetic, citric, malic and oxalic acid. Mean maximum amount of Pb in milliQ (mQ) water (1.8microM) was lower than in solutions from LMWOA alone or in combination with each other (i.e., mixed acid). However, there was no significant difference in the amount of Pb (and P) in solution in all treatments including mQ water after 6months. Among the 100microM LMWOA, mean of five highest soluble Pb (muM Pb in solution) followed the order: oxalic acid (17.6)>citric (6.2)>malic (5.6)>acetic acid (3.0microM Pb). Mixed acid solution had a maximum amount of 14.0microM Pb. We calculated a range of solubility product constant (K(sp)) of PY in this study from 8.6x10(-54) (mQ) to 7.0x10(-45)(oxalic acid); these values are within the range of PY K(sp) reported elsewhere. Despite the low K(sp) values, LMWOA-induced released Pb from PY are in concentrations higher than both Canadian and international drinking water and agricultural water use quality standards. This suggests that soil organic acids such as in rhizosphere can potentially liberate Pb from PY in contaminated soils.

Adsorption of Orange II dye in aqueous solution onto surfactant-coated zeolite: Characterization, kinetic and thermodynamic studies

Adsorption of anionic dye - Orange II - in aqueous solution onto hexadecyltrimethylammonium bromide (HDTMA)-coated zeolite (HCZ) reached 38.96mg/g compared with 8.13mg/g onto natural zeolite. Fourier Transform Infrared (FTIR), scanning electronic microscopy (SEM) and X-ray powder diffraction (XRD) data showed that HDTMA-coated zeolite developed surficial positive charges. The adsorption reaction fits the Freundlich isotherm (R(2)=0.93) and the value of 1/n was less than unity (=0.81) and suggest a multi-layer physi-sorption process. The kinetics of the adsorption is a pseudo-second-order model. The activation energy (Ea) of the reaction is +35.70kJ/mol to further support a physi-sorption process while the ΔH(o) (+82.79kJ/mol) is characteristic for an endothermic reaction. The ΔG(o) values of -2.33, -0.98 and -0.37kJ/mol at 25°C, 30°C and 35°C, respectively implied that the adsorption reaction was feasible and thermodynamically spontaneous. We proposed that both electrostatic interactions and partitioning process are involved in the adsorption mechanisms of Orange II dye onto HCZ.

Organic acids inhibit the formation of pyromorphite and Zn-phosphate in phosphorous amended Pb- and Zn-contaminated soil

Pyromorphite (PY) and some zinc phosphates (Zn-P) are very sparingly soluble minerals and hence can immobilize Pb and Zn in contaminated soils. However, mechanisms leading to the poor efficiency of PY and Zn-P formation in contaminated soils amended with P still remain unclear. We studied the influence of two low molecular weight organic acids (LMWOA) - oxalic acid and citric acid and diethylene triamine pentaacetic acid (DTPA) - in PY and Zn-P formation in a P-amended contaminated soil. Despite the high levels of metals (∼4% Pb and 21% Zn) in the study soil, the addition of up to 1% inorganic P transformed only up to 37% and 17% of the total Pb and Zn to PY and Zn-P, respectively. Semi-quantitative estimates from a linear combination fitting of X-ray absorption near edge spectra (LC-XANES fitting) showed that the formation of PY decreased from 37% to 3% of the total Pb in the presence of oxalic acid and the addition of 1% P. The reduced PY formation may be associated with the increase in organic-bound Pb from 9% to 54% and decrease in carbonate associated Pb from 42% to 12% with oxalic acid addition as indicated by a chemical sequential extraction (SE) technique. Citric acid seemed to have a less adverse effect in PY formation than oxalic acid. Our data also suggests both oxalic and citric acids have less adverse effects on the efficiency of Zn-P formation. From this study we conclude that the abundance of LMWOA in soil environments can be one factor contributing to the poor efficiency of P amendments practices to effectively immobilize Pb and Zn in metal contaminated soils.

Wood pellet fly ash and bottom ash as an effective liming agent and nutrient source for rye grass (Lolium perenne L.) and oats (Avena sativa)

Fly ash (FA) and bottom ash (BA) from a softwood pellet boiler were characterized and evaluated as soil amendments. In a greenhouse study, two plant species (rye grass, Lolium perenne L. and oats, Avena sativa) were grown in three different treatments (1% FA, 1% BA, non-amended control) of a silty loam soil. Total concentrations of plant nutrients Ca, K, Mg, P and Zn in both ashes were elevated compared to conventional wood ash. Concentrations of Cd, Cr, Pb, Se and Zn were found to be elevated in the FA relative to BA and the non-amended soil. At 28 d, oat above-ground biomass was found to be significantly greater in soil amended with FA. Potassium and Mo plant tissue concentrations were significantly increased by addition of either ash, and FA significantly increased Zn tissue concentrations. Cadmium and Hg tissue concentrations were elevated in some cases. As soil amendments, either pellet ash is an effective liming agent and nutrient source, but high concentrations of Cd and Zn in FA may preclude its use as an agricultural soil amendment in some jurisdictions. Lower ash application rates than those used in this study (i.e. <1%) may still provide sufficient nutrients and effective neutralization of soil acidity.

Increased biogas production in a wastewater treatment plant by anaerobic co-digestion of fruit and vegetable waste and sewer sludge - a full scale study.

Anaerobic digestion is a well established technology for the reduction of organic matter and stabilization of wastewater. Biogas, a mixture of methane and carbon dioxide, is produced as a useful by-product of the process. Current solid waste management at the city of Prince George is focused on disposal of waste and not on energy recovery. Co-digestion of fresh fruit and vegetable waste with sewer sludge can improve biogas yield by increasing the load of biodegradable material. A six week full-scale project co-digesting almost 15,000 kg of supermarket waste was completed. Average daily biogas production was found to be significantly higher than in previous years. Digester operation remained stable over the course of the study as indicated by the consistently low volatile acids-to-alkalinity ratio. Undigested organic material was visible in centrifuged sludge suggesting that the waste should have been added to the primary digester to prevent short circuiting and to increase the hydraulic retention time of the freshly added waste.

Toxic and non-toxic strains of Microcystis aeruginosa induce temperature dependent allelopathy toward growth and photosynthesis of Chlorella vulgaris

Global warming was believed to accelerate the expansion of cyanobacterial blooms. However, the impact of changes due to the allelopathic effects of cyanobacterial blooms with or without algal toxin production on the ecophysiology of its coexisting phytoplankton species arising from global warming were unknown until recently. In this study, the allelopathic effects of toxic and non-toxic Microcystis aeruginosa strains on the growth of green alga Chlorella vulgaris and photosynthesis of the co-cultivations of C. vulgaris and toxic M. aeruginosa FACHB-905 or non-toxic M. aeruginosa FACHB-469 were investigated at different temperatures. The growth of C. vulgaris, co-cultured with the toxic or non-toxic M. aeruginosa strains, was promoted at 20°C but inhibited at temperatures ≥25°C. The inhibitory effects of the toxic and non-toxic M. aeruginosa strains on of the co-cultivations (C. vulgaris and non-toxic M. aeruginosa FACHB-469 or toxic M. aeruginosa FACHB-905) also linearly increased with elevated temperatures. Furthermore, toxic M. aeruginosa FACHB-905 induced more inhibition toward growth of C. vulgaris or Pmax and Rd of the mixtures than non-toxic M. aeruginosa FACHB-469. C. vulgaris dominated over non-toxic M. aeruginosa FACHB-469 but toxic M. aeruginosa FACHB-905 overcame C. vulgaris when they were co-cultured in mesocosms in water temperatures from 20 to 25°C. The results indicate that allelopathic effects of M. aeruginosa strains on C. vulgaris are both temperature- and species-dependent: it was stimulative for C. vulgaris at low temperatures such as 20°C, but inhibitory at high temperatures (≥25°C); the toxic strain was determined to be more harmful to C. vulgaris than the non-toxic one. This suggests that global warming may aggravate the ecological risk of cyanobacteria blooms, especially those with toxic species as the main contributors.

Assessments of chromium (and other metals) in vegetables and potential bio-accumulations in humans living in areas affected by tannery wastes

Chromium (Cr) commonly enters the food chain through uptake by vegetables. However, accurate prediction of plant uptake of Cr (and other metals) still remains a challenge. In this study, we evaluated 5 indices of availability for Cr (and other metals) to identify reliable predictors of metal transfer from soils to garlic, onion, bokchoy, radish and celery grown in soils impacted by tannery wastes. The potential bio-accumulation of Cr in humans was calculated from the Cr content of vegetable predicted by the best bio-availability index, amounts of vegetable consumed and recommended daily doses for Cr. Our results show that soil total Cr is the best predictor of Cr transfer from soils to onion (Cr in onion=8.51+0.005 Total Cr) while Cr extractable by Synthetic Precipitation Leaching Procedure at pH 5 correlates very well with Cr uptake by bokchoy (Cr bokchoy=5.86+7.32 SPLP-5 Cr) and garlic (Cr garlic=7.63+2.36 SPLP-5 Cr). The uptake of Cr by radish and celery could not be reliably estimated by any of the 5 indices of availability tested in this study. Potential bio-accumulation of Cr in humans (BA-Cr) increases from soils with low Cr (BA-Cr=11.5) to soil with high total Cr (BA-Cr=31.3). Due to numerous soil factors affecting the behavior of Cr in soils and the physiological differences among vegetables, we suggest that the prediction of the transfer of Cr (and other metals) from soils to plants should be specific to site, metal and vegetable. Potential bio-accumulation of Cr in humans can be derived from a transfer function of Cr from soils to plants and the human consumption of vegetables.

Ultrasonic desorption of petroleum hydrocarbons from crude oil contaminated soils

Ultrasonic irradiation was applied to improve the desorption of petroleum hydrocarbons (PHC) in crude oil from three types of soil. Soil A was an Ottawa sand, while soil B and soil C were fine soils that contained 27.6% and 55.3% of silt and clay contents, respectively. It was found that the ultrasonic desorption was highly related to soil types, with the highest and the lowest desorption occurring in coarse soil (i.e., soil A) and finer soil (i.e., soil C), respectively. Under the experimental conditions, the maximum ultrasonic desorption enhancement of the total petroleum hydrocarbons (TPH) reached 22% for soil A, 61% for soil B, and 49% for soil C, respectively. The maximum enhancement on the F2 (n-C10 to n-C16), F3 (n-C16 to n-C34), and F4 (n-C34 to n-C50) fractions of PHC reached 91, 44, and 51% for soil B, and 90, 38, and 31% for soil C, respectively. The desorption enhancement also illustrated an increasing trend with initial soil TPH concentration.

An Eco-tank system containing microbes and different aquatic plant species for the bioremediation of N,N-dimethylformamide polluted river waters

An Eco-tank system of 10m was designed to simulate the natural river. It consisted of five tanks sequentially connected containing microbes, biofilm carriers and four species of floating aquatic plants. The purification performance of the system for N,N-dimethylformamide (DMF) polluted river water was evaluated by operating in continuous mode. DMF was completely removed in Tanks 1 and 2 at influent DMF concentrations between 75.42 and 161.05mg L-1. The NH4+-N concentration increased in Tank 1, followed by a gradual decrease in Tanks 2-5. Removal of NH4+-N was enhanced by aeration. The average effluent NH4+-N concentration of Tank 5 decreased to a minimum of 0.89mg L-1, corresponding to a decrease of 84.8% when compared with that before aeration. TN concentration did not decrease significantly as expected after inoculation with denitrifying bacteria. The average effluent TN concentration of the system was determined to be 4.58mg L-1, still unable to satisfy the Class V standard for surface water environmental quality. The results of this study demonstrated that the Eco-tank system is an efficient process in removing DMF, TOC, and NH4+-N from DMF polluted river water. However, if possible, alternative technologies should be adopted for controlling the effluent TN concentration.