Characterization of oily sludge from a wastewater treatment plant flocculation-flotation unit in a petroleum refinery and its treatment implications

Partly due to the complex and variable composition of oily sludge generated by the petroleum industry, cost-effective treatment and proper disposal pose considerable challenges worldwide. In this study, an extended component-based analysis of the oily sludge from a flocculation-flotation unit of a wastewater treatment system in a refinery in Sweden was carried out over 1 year. The heterogeneity of the oily sludge is illustrated by the wide ranges of concentrations found for different chemical components, particularly metals. Among the petroleum hydrocarbons, the most abundant compounds were nonpolar aliphatic hydrocarbons (63.7 ± 16.7 g kg⁻¹); from the benzene, toluene, ethylbenzene, and xylene group, xylenes (91–240 mg kg⁻¹) were most abundant; and among polycyclic aromatic hydrocarbons, naphthalene (25.7 ± 21.4), fluorene (27.25 ± 10.0), and phenanthrene (43.8 ± 18.4 mg kg⁻¹) were most abundant (all results in terms of dry matter). Based on the EU guidelines and the mean concentration values for metals found in the oily sludge, e.g., Pb (135.4 ± 125.8), Cu (105.2 ± 79.1), Hg (42.8 ± 31.3), Ni (320 ± 267.4), and Zn (1321.7 ± 529.9 mg kg⁻¹), disposal of oily sludge even in landfills for hazardous waste is not allowed. The organic content of the sludge can be reduced through biotreatment, but not the metal content. A multistep component-based treatment scheme is therefore needed.     

Selective adsorption of phenanthrene dissolved in surfactant solution using activated carbon

Selective adsorption of a hazardous hydrophobic organic compound (HOC) by activated carbon as a means of recovering surfactants after a soil washing process was investigated. As a model system, phenanthrene was selected as a representative HOC and Triton X-100 as a nonionic surfactant. Three activated carbons that differed in size (Darco 20–40 (D20), 12–20 (D12) and 4–12 (D4) mesh sizes) were used in adsorption experiments. Adsorption of surfactant onto activated carbon showed a constant maximum above the critical micelle concentration, which were 0.30, 0.23, 0.15 g g⁻¹ for D20, D12, and D4, respectively. Selectivity for phenanthrene to Triton X-100 was much higher than 1 over a wide range of activated carbon doses (0–6 g l⁻¹) and initial phenanthrene concentrations (10–110 mg l⁻¹). Selectivity generally increased with decreasing particle size, increasing activated carbon dose, and decreasing initial concentration of phenanthrene. The highest selectivity was 74.9, 57.3, and 38.3 for D20, D12, and D4, respectively, at the initial conditions of 10 mg l⁻¹ phenanthrene, 5 g l⁻¹ Triton X-100 and 1 g l⁻¹ activated carbon. In the case of D20 at the same conditions, 86.5% of the initial phenanthrene was removed by sorption and 93.6% of the initial Triton X-100 remained in the solution following the selective adsorption process. The results suggest that the selective adsorption by activated carbon is a good alternative for surfactant recovery in a soil washing process.     

The effects of dissolved organic matter and pH on sampling rates for polar organic chemical integrative samplers (POCIS)

The effect of solution pH and levels of dissolved organic matter (DOM) on the sampling rates for model pharmaceuticals and personal care products (PPCPs) and endocrine disrupting substance (EDS) by polar organic chemical integrative samplers (POCIS) was investigated in laboratory experiments. A commercially available POCIS configuration containing neutral Oasis HLB (hydrophilic-lipophilic balance) resin (i.e. pharmaceutical POCIS) and two POCIS configurations prepared in-house containing MAX and MCX anion and cation exchange resins, respectively were tested for uptake of 21 model PPCPs and EDS, including acidic, phenolic, basic and neutral compounds. Laboratory experiments were conducted with dechlorinated tap water over a pH range of 3, 7 and 9. The effects of DOM were studied using natural water from an oligotrophic lake in Ontario, Canada (i.e. Plastic Lake) spiked with different amounts of DOM (the concentration of dissolved organic carbon ranged from 3 to 5 mg L⁻¹ in uptake experiments). In experiments with the commercial (HLB) POCIS, the MCX-POCIS and the MAX-POCIS, the sampling rates generally increased with pH for basic compounds and declined with pH for acidic compounds. However, the sampling rates were relatively constant across the pH range for phenols with high pKa values (i.e. bisphenol A, estrone, estradiol, triclosan) and for the neutral pharmaceutical, carbamazepine. Thus, uptake was greatest when the amount of the neutral species in solution was maximized relative to the ionized species. Although the solution pH affected the uptake of some model ionic compounds, the effect was by less than a factor of 3. There was no significant effect of DOM on sampling rates from Plastic Lake. However, uptake rates in different aqueous matrixes declined in the order of deionized water > Plastic Lake water > dechlorinated tap water, so other parameters must affect uptake into POCIS, although this influence will be minor. MAX-POCIS and MCX-POCIS showed little advantage over the commercial POCIS configuration for monitoring in natural waters.     

兰州市大气降尘中PAHs分布与生态风险评价

对兰州市春季不同功能区大气降尘有机质中多环芳烃（PAHs）种类进行分析,采用GC／MS法检出了大气降尘中有机质USEPA优控PAHs有11种以上,含量较高的集中于萘（NAP）、荧蒽（FLUA）、菲（PHE）、芘（PYR）、[艹屈]（CHR）,占各采样点PAHs总量的70％以上。源解析表明兰州市各功能区大气降尘PAHs来源不仅有较高的燃煤源、交通源（汽车尾气）,同时PAHs的组成与分布也在很大程度上受到采样点周围居民居住环境的影响。对照有关的沉积物质量标志水平,兰州市城关区各站点都有PAHs浓度超出相应质量警戒水平,属高生态风险区     

Effect of fuel composition and engine operating conditions on polycyclic aromatic hydrocarbon emissions from a fleet of heavy-duty diesel buses

Emissions from 12 in-service heavy-duty buses powered by low- (LSD) and ultra low-sulfur (ULSD) diesel fuels were measured with the aim to characterize the profile of polycyclic aromatic hydrocarbons (PAHs) in the exhaust and to identify the effect of different types of fuels on the emissions. To mimic on-road conditions as much as possible, sampling was conducted on a chassis dynamometer at four driving modes, namely: mode 7 or idle (0% power), mode 11 (25% power), mode 10 (50% power) and mode 8 (100% power). Irrespective of the type of fuel used, naphthalene, acenaphthene, acenaphthylene, anthracene, phenanthrene, fluorene, fluoranthene and pyrene were found to be the dominant PAHs in the exhaust emissions of the buses. However, the PAH composition in the exhausts of ULSD buses were up to 91±6% less than those in the LSD buses. In particular, three- and four-ringed PAHs were more abundant in the later than in the former. Lowering of fuel sulfur content not only reduced PAH emission, but also decreased the benzo(a)pyrene equivalent (BAP_eq) and hence the toxicity of the exhaust. Result from multicriteria decision-making and multivariate data analysis techniques showed that the use of ULSD afforded cleaner exhaust compositions and emissions with characteristics that are distinct from those obtained by the use of LSD.     

Effects of cowpea (Vigna unguiculata) root mucilage on microbial community response and capacity for phenanthrene remediation

Biodegradation of polycyclic aromatic hydrocarbons (PAHs) is normally limited by their low solubility and poor bioavailability. Prior research suggests that biosurfactants are synthesized as intermediates during the production of mucilage at the root tip. To date the effects of mucilage on PAH degradation and microbial community response have not been directly examined. To address this question, our research compared 3 cowpea breeding lines (Vigna unguiculata) that differed in mucilage production for their effects on phenanthrene (PHE) degradation in soil. The High Performance Liquid Chromatography results indicated that the highest PHE degradation rate was achieved in soils planted with mucilage producing cowpea line C1, inoculated with Bradyrhizobium, leading to 91.6% PHE disappearance in 5 weeks. In root printing tests, strings treated with mucilage and bacteria produced larger clearing zones than those produced on mucilage treated strings with no bacteria or bacteria inoculated strings. Experiments with ¹⁴C-PHE and purified mucilage in soil slurry confirmed that the root mucilage significantly enhanced PHE mineralization (82.7%), which is 12% more than the control treatment without mucilage. The profiles of the PHE degraders generated by Denaturing gradient gel electrophoresis suggested that cowpea C1, producing a high amount of root mucilage, selectively enriched the PHE degrading bacteria population in rhizosphere. These findings indicate that root mucilage may play a significant role in enhancing PHE degradation and suggests that differences in mucilage production may be an important criterion for selection of the best plant species for use in phytoremediation of PAH contaminated soils.     

Temperature dependence of the heterogeneous uptake of acrylic acid on Arizona test dust

In this study, the temperature dependence of the heterogeneous uptake of acrylic acid on Arizona test dust(ATD) has been investigated within a temperature range of 255–315 K using a Knudsen cell reactor. Combined with diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS) experiment, it was found that acrylic acid could adsorb on ATD via surface OH groups and convert to carboxylate on the particle surface. The kinetics study suggests that the initial true uptake coefficient(γt) of acrylic acid on ATD decreases from(4.02 ± 0.12) × 10~(-5) to(1.73 ± 0.05) × 10~/(-5)with a temperature increase from 255 to315 K. According to the temperature dependence of uptake coefficients, the enthalpy(ΔH obs)and entropy(ΔS obs) of uptake processes were determined to be-(9.60 ± 0.38) KJ/mol and-(121.55 ± 1.33) J·K/mol, respectively. The activation energy for desorption(E des) was calculated to be(14.57 ± 0.60) KJ/mol. These results indicated that the heterogeneous uptake of acrylic acid on ATD surface was sensitive to temperature. The heterogeneous uptake on ATD could affect the concentration of acrylic acid in the atmosphere, especially at low temperature.     

Uptake of Cd(II) and Pb(II) by microalgae in presence of colloidal organic matter from wastewater treatment plant effluents

The present study addresses the key issue of linking the chemical speciation to the uptake of priority pollutants Cd(II) and Pb(II) in the wastewater treatment plant effluents, with emphasis on the role of the colloidal organic matter (EfOM). Binding of Cd(II) and Pb(II) by EfOM was examined by an ion exchange technique and flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry in parallel to bioassays with green microalga Chlorella kesslerii in ultrafiltrate (<1 kDa) and colloidal isolates (1 kDa to 0.45 μm). The uptake of Cd by C. kesslerii was consistent with the speciation analysis and measured free metal ion concentrations, while Pb uptake was much greater than that expected from the speciation measurement. Better understanding of the differences in the effects of the EfOM on Cd(II) and Pb(II) uptake required to take into account the size dependence of metal binding by EfOM.     

Determination of polycyclic aromatic hydrocarbons in roasted coffee

Polycyclic aromatic hydrocarbons (PAHs) are suspected to be carcinogenic and mutagenic. This study describes the presence of PAHs in light, medium and dark roasted coffee including instant and decaffeinated brands. Total PAHs concentration was related to the degree of roasting with light roasted coffee showing the least and dark roasted coffee showing the highest level. Both instant and decaffeinated coffee brand showed lower levels of PAHs. Naphthalene, acenaphthylene, pyrene and chrysene were the most abundant individual isomers. The concentrations ranged from 0 to 561 ng g^?1 for naphthalene, 0 to 512 ng g^?1 for acenaphthylene, 60 to 459 ng g^?1 for pyrene and 56 to 371 ng g^?1 for chrysene. Thus, roasting conditions should be controlled to avoid the formation of PAHs due to their suspected carcinogenic and mutagenic properties.     

Monitoring of fuel consumption and aromatics formation in a kerosene spray flame as characterized by fluorescence spectroscopy

The large presence of aromatic compounds in distillate fossil fuels should allow, in line of principle, to follow the fuel consumption and/or the presence of unburned fuel in a high temperature environment like a burner or the exhaust of combustion systems by exploiting the high fluorescence emission of aromatic fuel components. To this aim an UV-excited fluorescence source has to be used since the aromatic fuel components are strongly fluorescing in the UV region of the emission spectrum.

In this work UV-excited laser induced fluorescence (LIF) diagnostics was applied to spray flames of kerosene in order to follow the fuel consumption and the formation of aromatic species. A strong UV signal was detected in the spray region of the flame that presented a shape similar to that found in the LIF spectra preliminary measured on the cold spray and in the room-temperature fluorescence of fuel solutions.

The decrease of UV signal along the spray flame region was associated to the consumption of the fuel, but more difficult seems to be the attribution of a broad visible emission, that is present downstream of the flame.

The visible emission feature could be assigned to flame-formed PAH species contained in the high molecular weight species, hypothesizing that their fluorescence spectra are shifted toward the visible for effect of the high temperature flame environment.