Determination of total and available fractions of PAHs by SPME in oily wastewaters: overcoming interference from NAPL and NOM

Background, aim, and scope  

Polycyclic aromatic hydrocarbons (PAHs) are often found in oily wastewaters. Their presence is usually the result of human activities and has a negative effect on the environment. One important step in addressing this problem is to evaluate the effectiveness of PAH removal by biological processes since these are the most cost-effective treatments known today. Many techniques are presently available for PAH determination in wastewaters. Solid phase microextracion (SPME) is known to be one of the most effective techniques for this purpose. When analyzing complex matrices with substances such as natural organic matter (NOM) and non-aqueous phase liquids (NAPL), it is important to differentiate the free dissolved PAH from matrix-bonded PAH. PAHs associated with the bonded fraction are less susceptible to biological treatment. The present study concerns the development of a simple and suitable methodology for the determination of the freely dissolved and the total fraction of PAHs present in oily wastewaters. The methodology was then applied to an oily wastewater from a fuel station retention basin.     

Effect of impeller type and mechanical agitation on the mass transfer and power consumption aspects of ASBR operation treating synthetic wastewater

The effect of flow type and rotor speed was investigated in a round-bottom reactor with 5 L useful volume containing 2.0 L of granular biomass. The reactor treated 2.0 L of synthetic wastewater with a concentration of 800 mgCOD/L in 8-h cycles at 30 degrees C. Five impellers, commonly used in biological processes, have been employed to this end, namely: a turbine and a paddle impeller with six-vertical-flat-blades, a turbine and a paddle impeller with six-45 degrees -inclined-flat-blades and a three-blade-helix impeller. Results showed that altering impeller type and rotor speed did not significantly affect system stability and performance. Average organic matter removal efficiency was about 84% for filtered samples, total volatile acids concentration was below 20 mgHAc/L and bicarbonate alkalinity a little less than 400 mgCaCO3/L for most of the investigated conditions. However, analysis of the first-order kinetic model constants showed that alteration in rotor speed resulted in an increase in the values of the kinetic constants (for instance, from 0.57 h(-1) at 50 rpm to 0.84 h(-1) at 75 rpm when the paddle impeller with six-45 degrees -inclined-flat-blades was used) and that axial flow in mechanically stirred reactors is preferable over radial-flow when the vertical-flat-blade impeller is compared to the inclined-flat-blade impeller (for instance at 75 rpm, from 0.52 h(-1) with the six-flat-blade-paddle impeller to 0.84 h(-1) with the six-45 degrees -inclined-flat-blade-paddle impeller), demonstrating that there is a rotor speed and an impeller type that maximize solid-liquid mass transfer in the reaction medium. Furthermore, power consumption studies in this reduced reactor volume showed that no high power transfer is required to improve mass transfer (less than 0.6 kW/10(3)m3).     

Concentrations of PCDD/Fs,PCBs and PBDEs in breast milk of women from Catalonia,Spain: A follow-up study

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) were determined in breast milk from women living in the vicinity of a new hazardous waste incinerator (HWI) in Catalonia, Spain. The results were compared with the levels obtained in two previous surveys carried out in 1998 (baseline study) and 2002. The current concentrations of PCDD/Fs in breast milk ranged from 45 to 143 pg/g fat (2.8 to 11.2 pg WHO-TEQ/g fat), while total PCBs ranged from 114 to 617 pg/g fat (2.8 to 17.6 pg WHO-TEQ/g fat). PBDE concentrations (sum 15 congeners) ranged from 0.57 ng/g fat to 5.9 ng/g fat, with a mean value of 2.5 ng/g fat. A general decrease of the concentrations for PCDD/Fs and both planar and total PCBs was observed. Regarding to PBDE concentrations in breast milk, similar levels between the 2002 and the present study were noted. The levels of PCDD/Fs and PCBs in milk of women living in urban areas were higher than those corresponding to the industrial zones (38% and 40%, respectively). However, the current PBDE levels were slightly lower (13%) in the urban than in the industrial zone. For PCDD/Fs and PCBs, the current decreases are in accordance with the reduction in the dietary intake of these pollutants found in recent studies carried out in the same area of study.     

Spatial and temporal variations in inhalable CuZnPb aerosols within the Mexico City pollution plume

We report on the CuPbZn content of PM10 and PM2.5 samples collected from three sites (urban T0, suburban T1 and rural T2) during the Mexico City MILAGRO campaign of March 2006. Daytime city centre concentrations of summation operator CuZnPb(PM10) were much higher (T0 > 450 ng m(-3)) than at the suburban site (T1 < 200 ng m(-3)). Rural site (T2) summation operator CuZnPb(PM10) concentrations exceeded 50 ng m(-3) when influenced by the megacity plume but dropped to 10 ng m(-3) during clean northerly winds. Nocturnal metal concentrations more than doubled at T0, as pollutants became trapped in the nightly inversion layer, but decreased at the rural site. Transient spikes in concentrations of different metals, e.g. a "copper event" at T0 (CuPM10 281 ng m(-3)) and "zinc event" at T1 (ZnPM10 1481 ng m(-3)) on the night of March 7-8, demonstrate how industrial pollution sources produce localised chemical inhomogeneities in the city atmosphere. Most metal aerosols are <2.5 microm and SEM study demonstrates the dominance of Fe, Ti, Ba, Cu, Pb and Zn (and lesser Sn, Mo, Sb, W, Ni, V, As, Bi) in metalliferous particles that have shapes including spherical condensates, efflorescent CuZnClS particles, cindery Zn, and Cu wire. Metal aerosol concentrations do not change in concert with PM10 mass, which is more influenced by wind resuspension than industrial emissions. Metalliferous particles can induce cell damage, and PM composition is probably more important than PM mass, with respect to negative health effects, so that better monitoring and control of industrial emissions would likely produce significant improvements in air quality.     

Metal levels in sediments from the Minho estuary salt marsh: a metal clean area?

Total-recoverable metals (Al, Cr, Cu, Fe, Mn, Ni, Pb and Zn) in sediments from Minho estuary salt marsh were determined to evaluate possible increase in anthropogenic contamination by metals and to evaluate the possibility of this area to be considered a pristine area in terms of metals, which can be used as a reference site for other metal-contaminated national and international estuaries/salt marshes. This study revealed that the spatial distribution of metals in the salt marsh sediments was not homogeneous and that two sampling sites (sites 5 and 7) had indications of anthropogenic contamination. However, metal levels in these salt marsh sediments were lower than those observed in the wetlands of the main Portuguese estuaries. Comparison with Portuguese and international reference values used in the evaluation of the ecological quality of sediments, indicated that the sediments can be classified as “clean sediment” and that metal levels were lower or similar (only for Cu and Ni) to the values of ERL, which are the values that define the concentrations ranges that are rarely associated to adverse biologic effects in organisms. In addition, metal levels in the sediments were in chemical forms that were not easily available to organisms, indicating that these sediments probably will not have negative influences in the organisms living in the salt marsh, although no life-form ecological safety tests have been carried out. Therefore, the Minho estuary salt marsh area can probably be considered a pristine area in terms of metals and can be used as a reference for other metal-contaminated estuaries/salt marshes.     

Effects of municipal solid waste compost and sewage sludge on chemical and spectroscopic properties of humic acids from a sandy Haplic Podzol and a clay loam Calcic Vertisol in Portugal

The effects of amendment with municipal solid waste compost (MSWC) and anaerobically digested sewage sludge (SS) on the compositional and structural features of soil humic acids (HAs) were investigated. For this purpose, HAs were isolated from MSWC, SS, and two different Portuguese soils, a sandy Haplic Podzol and a clay loam Calcic Vertisol, which were either unamended or amended with MSWC or SS at a rate of 60tha(-1). The isolated HAs were analyzed for elemental and acidic functional group composition, and by ultraviolet/visible, Fourier transform infrared (FT IR), and fluorescence spectroscopies. The application of MSWC and especially SS to soils determined an increase of C, N, H, and S contents and E(4)/E(6) ratios (i.e., ratios of absorbances at 465 and 665nm), and a decrease of O, COOH, and phenolic OH contents and C/N, C/H, and O/C ratios of soil HAs. The FT IR and fluorescence results showed that the organic amendments, especially SS, caused an increase of the aliphatic character and a decrease of the degrees of aromatic polycondensation, polymerization, and humification of amended soil HAs. Both MSWC and SS affected more markedly the clayey soil HAs than the sandy soil HAs, possibly due to less extended mineralization processes and the protective action of clay minerals on amended soil HAs.     

Arsenic removal from water employing heterogeneous photocatalysis with TiO2 immobilized in PET bottles

Arsenic oxidation (As(III) to As(V)) and As(V) removal from water were assessed by using TiO₂ immobilized in PET (polyethylene terephthalate) bottles in the presence of natural sunlight and iron salts. The effect of many parameters was sequentially studied: TiO₂ concentration of the coating solution, Fe(II) concentration, pH, solar irradiation time; dissolved organic carbon concentration. The final conditions (TiO₂ concentration of the coating solution: 10%; Fe(II): 7.0 mg l⁻¹; solar exposure time: 120 min) were applied to natural water samples spiked with 500 μg l⁻¹ As(III) in order to verify the influence of natural water matrix. After treatment, As(III) and total As concentrations were lower than the limit of quantitation (2 μg l⁻¹) of the voltammetric method used, showing a removal over 99%, and giving evidence that As(III) was effectively oxidized to As(V). The results obtained demonstrated that TiO₂ can be easily immobilized on a PET surface in order to perform As(III) oxidation in water and that this TiO₂ immobilization, combined with coprecipitation of arsenic on Fe(III) hydroxides(oxides) could be an efficient way for inorganic arsenic removal from groundwaters.     

Air concentrations of PCDD/Fs, PCBs and PCNs using active and passive air samplers

The concentrations of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) were determined in air samples collected at four sampling sites located in two zones of Barcelona (Spain): near a municipal solid waste incinerator (MSWI) and a combined cycle power plant (3 sites), and at a background/control site. Samples were collected using high-volume active samplers. Moreover, 4 PUF passive samplers were deployed at the same sampling points during three months. For PCDD/Fs, total WHO-TEQ values were 27.3 and 10.9 fg WHO-TEQm(-3) at the urban/industrial and the background sites, respectively. The sum of 7 PCB congeners and the Sigma PCN levels were also higher at the industrial site than at the background site. In order to compare active and passive sampling, the accumulated amounts of PCDD/Fs, PCBs and PCNs in the four passive air samplers, as well as the total toxic equivalents in each sampling site were also determined. To assess the use of PUF passive samplers as a complementary tool for PCDD/F, PCB and PCN monitoring, sampling rates were calculated in accordance with the theory of passive air samplers. PUF disks allowed establishing differences among zones for the POP levels, showing that they can be a suitable method to determine POP concentrations in air in areas with various potential emission sources. Although both particle and gas phase were sorbed by the PUFs, data of gas phase congeners are more reproducible.     

Microbial community dynamics in a chemolithotrophic denitrification reactor inoculated with methanogenic granular sludge

Denitrification is applied in the tertiary treatment of wastewater to reduce nitrogen pollution. Fluorescence in situ hybridization (FISH), catalyzed reporter deposition (CARD)-FISH, cloning, and scanning electron microscopy (SEM) were applied to follow the evolution of the microbial composition and structure of granular sludge in chemolithotrophic denitrifying bioreactors fed with nitrate and thiosulfate. FISH oligonucleotide probes for the chemolitoautotrophic denitrifiers Thiobacillus denitrificans and Thiomicrospira denitrificans were designed and their utility tested. CARD-FISH and cloning data showed that bacterial diversity in the biofilms changed during the reactor operation. Chemoorganotrophic fermentative Gram-positive strains in the phyla, Actinobacteria and Firmicutes, were dominant in the methanogenic inoculum, both in terms of biodiversity and in number. Other significant phyla were Bacteroidetes and Chloroflexi. After 6 months of operation, Proteobacteria became dominant (83% of the clones). The diversity of Gram-positive bacteria was partially maintained although their abundance decreased notably. After 110 d of operation, the abundance of Tb. denitrificans cells increased considerably, from 1% to 35% of total DAPI-stained cells and from no isolated clones to 15% of the total clones. Tm. denitrificans only represented a minor fraction of the microorganisms in the sludge (1-4% of the DAPI-stained cells). These findings confirm that Tb. denitrificans was the dominant chemolitoautotrophic denitrifying microorganism in the bioreactors. The Archaeal diversity remained almost unchanged and it was represented mostly by Methanosaeta soehngenii. SEM results indicated a considerable loss in the integrity of the sludge granules during the operation, with risk of sludge buoyancy.