Heavy metal removal from synthetic wastewaters in an anaerobic bioreactor using stillage from ethanol distilleries as a carbon source

This work was conducted to investigate the possibility of using stillage from ethanol distilleries as substrate for sulfate reducing bacteria (SRB) growth and to evaluate the removal efficiency of heavy metals present in wastewaters containing sulfates. The experiments were carried out in a continuous bench-scale Upflow Anaerobic Sludge Blanket reactor (13 l) operated with a hydraulic retention time of 18 h. The bioreactor was inoculated with 7 l of anaerobic sludge. Afterwards, an enrichment procedure to increase SRB numbers was started. After this, cadmium and zinc were added to the synthetic wastewater, and their removal as metal sulfide was evaluated. The synthetic wastewater used represented the drainage from a dam of a metallurgical industry to which a carbon source (stillage) was added. The results showed that high percentages of removal (>99%) of Cd and Zn were attained in the bioreactor, and that the removal as sulfide precipitates was not the only form of metal removal occurring in the bioreactor environment.     

Biological nitrogen and carbon removal in a gravity flow biomass concentrator reactor for municipal sewage treatment

A novel membrane system, the Biomass Concentrator Reactor (BCR), was evaluated as an alternative technology for the treatment of municipal wastewater. Because the BCR is equipped with a membrane whose average poresize is 20 μm (18–28 μm), the reactor requires low-pressure differential to operate (gravity). The effectiveness of this system was evaluated for the removal of carbon and nitrogen using two identical BCRs, identified as conventional and hybrid, that were operated in parallel. The conventional reactor was operated under full aerobic conditions (i.e., organic carbon and ammonia oxidation), while the hybrid reactor incorporated an anoxic zone for nitrate reduction as well as an aerobic zone for organic carbon and ammonia oxidation. Both reactors were fed synthetic wastewater at a flow rate of 71 L d^?1, which resulted in a hydraulic retention time of 9 h. In the case of the hybrid reactor, the recycle flow from the aerobic zone to the anoxic zone was twice the feed flow rate. Reactor performance was evaluated under two solids retention times (6 and 15 d). Under these conditions, the BCRs achieved nearly 100% mixed liquor solids separation with a hydraulic head differential of less than 2.5 cm. The COD removal efficiency was over 90%. Essentially complete nitrification was achieved in both systems, and nitrogen removal in the hybrid reactor was close to the expected value (67%).     

Engine dynamometer experiments: platinum emissions from differently aged three-way catalytic converters

Depending on the operating conditions and the age of the converter, mean platinum emissions ranged from 7 to 123 ng m^-3 corresponding to emission factors between 9 and 124 ng km^-1. There were no statistically significant differences between the four converter brands tested. The data from new (12–90 ng km^-1) and old catalytic converters (9–26 ng km^-1) installed on a medium-powered gasoline engine (1.8 l 66 kW) showed a tendency towards decreasing platinum emission with increasing use. The platinum emissions increased with rising simulated speed and exhaust temperature. The lowest mean emission from new converters (12 ng km^-1) was found at a constant speed of 80 km h^-1, the highest (90 ng km^-1) at 130 km h^-1. Using the US72 or the US72-EUDC test cycles the emission factors were higher (37 or 19 ng km^-1) than at 80 km h^-1 indicating that additional mechanical or thermal impacts enhance the platinum abrasion at cycle conditions. After installing catalytic converters tested with the 1.8 l engine on a smaller engine (1.4 l 44 kW), the platinum emissions measured at the US72 cycle and a high-speed condition (140 km h^-1) were only 9 and 22 ng km^-1, respectively. Platinum is almost exclusively emitted bound to aluminum oxide particles where (depending on the driving conditions) 43–74% of these emitted particles had aerodynamic diameters >10 μm. The alveolar fraction (<3 μm) was between 11 and 26% (1.8 l engine) and between 21 and 36% (1.4 l engine). If at all, soluble platinum is emitted in only very small quantities (⩽1%).     

Occurrence and fate of the human pharmaceutical metabolite ritalinic acid in the aquatic system

To investigate the occurrence and fate of ritalinic acid – the main human metabolite of the psychostimulant drug methylphenidate – in the aquatic environment, a HPLC–electrospray–MS/MS method for the quantification of ritalinic acid in wastewater, surface water and bank filtrate was developed. Carbamazepine known as very stable in the aquatic environment was analyzed as anthropogenic marker in parallel. Furthermore, the removal of ritalinic acid was studied in a sewage treatment plant using an activated sludge system during a field study and in lab-scale plants. In good agreement between lab-scale and field studies a low removal rate of 13% and 23%, respectively, was determined. As a consequence, the concentration of ritalinic acid in the wastewater effluents were in the range of <50–170 ng L⁻¹ which corresponds to a mean specific load per capita of 17.7 μg d⁻¹.Ritalinic acid has further been detected in German rivers at concentrations of 4–23 ng L⁻¹ and in bank filtrate samples in 100–850 m distance from the river up to 5 ng L⁻¹ demonstrating the widespread occurrence of this stable metabolite in the aquatic environment. A comparison to available sales data shows that a significant amount of methylphenidate applied can be found in waters as ritalinic acid.     

Detection,occurrence and fate of 22 psychiatric pharmaceuticals in psychiatric hospital and municipal wastewater treatment plants in Beijing,China

The liquid chromatography–electrospray ionization-tandem mass spectrometer (LC–MS/MS) method coupled with an automated solid-phase extraction procedure has been developed to identify 22 psychiatric pharmaceuticals, including seven anxiolytic-sedative-hypnotics, six antidepressants, and nine anti-schizophrenia drugs, in wastewater samples from two psychiatric hospital wastewater treatment plants (P-WWTPs) and three municipal wastewater treatment plants (M-WWTPs) in Beijing, China. Analyte recoveries from spiking experiments in the WWTP influent and effluent at three concentrations ranged from 70% to 110%, excluding sulpiride, ziprasidone, and olanzapine. Method detection limits for five, eight, and nine analytes in the WWTP influent and effluent were 20–80, 1–16, and <1 ng L^?1, respectively. High psychiatric pharmaceutical concentrations (e.g., ～942 ng L^?1oxazepam, 5552–12,782 ng L^?1 clozapine, 2762–9832 ng L^?1sulpiride, and 2030–4967 ng L^?1quetiapine) were frequently observed in P-WWTP influent compared to M-WWTPs. Although P-WWTPs typically had higher removal rates, significantly higher concentrations of the target compounds were observed in the P-WWTP secondary effluent than in the M-WWTP influent (e.g., ～752 ng L^?1oxazepam, ～8183 ng L^?1 clozapine, ～10,833 ng L^?1sulpiride, and ～1168 ng L^?1quetiapine). Thus, the discharge control of psychiatric pharmaceuticals from psychiatric hospitals requires improvement.     

Accumulation and leaching potential of some pharmaceuticals and potential endocrine disruptors in soils irrigated with wastewater in the Tula Valley,Mexico

The reuse of wastewater for irrigation of agricultural land is a well established practice but introduces many contaminants into the terrestrial environment including pharmaceuticals and personal care products. This study reports the persistence and leaching potential of a group of acidic pharmaceuticals, carbamazepine, and three endocrine disruptors in soils from the Tula Valley in Mexico, one of the largest irrigation districts in the world that uses untreated wastewater. After irrigation of soil columns with fortified wastewater over the equivalent of one crop cycle, between 0% and 7% of the total added amounts of ibuprofen, naproxen, and diclofenac and between 0% and 25% of 4-nonylphenol, triclosan, and bisphenol-A were recovered from the soil profiles. Carbamazepine was more persistent, between 55% and 107% being recovered. Amounts in leachates suggested that movement through the soil was possible for all of the analytes, particularly in profiles of low organic matter and clay content. Analysis of soil samples from the Tula Valley confirmed the general lack of accumulation of the acidic pharmaceuticals (concentrations from below the limit of detection to 0.61 μg kg⁻¹) and endocrine disruptors (concentrations from below the limit of detection to 109 μg kg⁻¹) despite continual addition through regular irrigation with untreated wastewater; there was little evidence of movement through the soil profiles. In contrast, carbamazepine was present in horizon A of the soil at concentrations equivalent to several years of additions by irrigation (2.6–7.5 μg kg⁻¹) and was also present in the deeper horizons. The persistence and mobility of carbamazepine suggested a potential to contaminate groundwater.     

Manometric study of CO2 and H2S emission from aqueous solutions and wastewater

The emissions of CO₂ and H₂S from the aqueous solutions and wastewater were studied to determine and compare the times required to reach the equilibrium of H₂S and CO₂ between water and gas phases. The solutions of NaHCO₃ and NaHS were acidified and the change in the pressure of emitted gases was measured with a manometric OxiTop^® system. The average time required to achieve the equilibrium state of distribution of CO₂ between two phases was 16.7±1.5 min, and it did not depend on the initial amount of NaHCO₃ in the solution. The average time required to achieve the equilibrium of H₂S (sulfide) was 19.5±5.5 min, having the same value for solutions with different initial contents of sulfide ions. The average time required to achieve the equilibrium of H₂S in the wastewater was 16.2±3.6 min, and it showed the faster emission of gaseous H₂S to decrease the oversaturation of the solution. The ratio of measured values of pressure to the calculated values did not depend on the concentration of NaHS in the initial solution, and its average value was 0.86±0.14. The results showed that measured values of pressure of H₂S emitted from the wastewater were twice lower than the calculated values and it is necessary to take into account the catalyzed formation of polysulfide in the solution of sulfides.     

Production and partial characterization of bioemulsifier from a chromium-resistant actinobacteria

Surface-active compounds such as synthetic emulsifiers have been used for several decades, both for the degradation of hydrocarbons and increasing desorption of soil-bound metals. However, due to their high toxicity, low degradability, and production costs unaffordable for use in larger ecosystems, synthetic emulsifiers have been gradually replaced by those derived from natural sources such as plants or microbes. In previous studies, the bacterium Streptomyces sp. MC1 has shown the ability to reduce and/or accumulate Cr(VI), a highly promising advance in the development of methods for environmental clean-up of sites contaminated with chromium. Here, new studies on the production of emulsifier from this strain are presented. The cultivation factors that have a significant influence on emulsifier biosynthesis, as well as the interactions among them, were studied by factorial design. Based upon optimization studies, maximum bioemulsifier production was detected in the culture medium having an initial pH of 8 with phosphate 2.0 g L^?1 and Ca⁺² 1.0 g L^?1 added, with an emulsification index about 3.5 times greater compared to the basal value. Interestingly, in the presence of 5.0 g L^?1 Cr(VI), Streptomyces sp. MC1 retained about 65% of its emulsifier production ability. Partially purified emulsifier presented high thermo-stability and partial water solubility. These findings could have promising future prospects for the remediation of organic- and metal-contaminated sites.     

Sulfuric odorous compounds emitted from pig-feeding operations

The objective of the study was to quantify the concentration and emission levels of sulfuric odorous compounds emitted from pig-feeding operations. Five types of pig-housing rooms were studied: gestation, farrowing, nursery, growing and fattening rooms. The concentration range of sulfuric odorous compounds in these pig-housing rooms were 30–200 ppb for hydrogen sulfide (H₂S), 2.5–20 ppb for methyl mercaptan (CH₃SH), 1.5–12 ppb for dimethyl sulfide (DMS; CH₃SCH₃) and 0.5–7 ppb for dimethyl disulfide (DMDS; CH₃S₂CH₃), respectively. The emission rates of H₂S, CH₃SH, DMS and DMDS were estimated by multiplying the average concentration (mg m⁻³) measured near the air outlet by the mean ventilation rate (m³ h⁻¹) and expressed either per area (mg m⁻² h⁻¹) or animal unit (AU; liveweight of the pig, 500 kg) (mg pig⁻¹ h⁻¹). As a result, the emission rates of H₂S, CH₃SH, DMS and DMDS in the pig-housing rooms were 14–64, 0.8–7.3, 0.4–3.4 and 0.2–1.9 mg m⁻² h⁻¹, respectively, based on pig's activity space and 310–723, 18–80, 9–39 and 5–22 mg AU⁻¹ h⁻¹, respectively, based on pig's liveweight, which indicates that their emission rates were similar, whether based upon the pig's activity space or liveweight. In conclusion, the concentrations and emission rates of H₂S were highest in the fattening room followed by the growing, nursery, farrowing and gestation rooms whereas those of CH₃SH, DMS and DMDS concentrations were largest in the growing room followed by the nursery, gestation and farrowing rooms.     

Biogenic nitric oxide from wastewater land application

The importance of municipal wastewater land application to nitric oxide production and transport in soil was studied through the formulation and conduct of a comprehensive laboratory testing protocol. Nitric oxide (NO) is a precursor in the formation of tropospheric ozone which can directly impact public health and the environment. It is the uncertainty in the NO budget, and its relation to O₃, that motivates the need for measurements and modeling of NO flux from soils. Wastewater-amended soil is potentially one important component of that budget. NO emissions reported here were measured from: a well-characterized unamended soil, water-amended soil, and wastewater-amended soil in the laboratory in a dynamic test chamber. Laboratory results indicate that NO emissions from the selected sandy loam soil ranged from 0.3 to 0.4 ng N m^-2 s^-1 per cm² of unamended soil, while water-amended soil emissions ranged from 0.4 to 0.7 ng N m^-2 s^-1 per cm². NO flux from wastewater-amended soil ranged from 1.0 to 1.2 ng N m^-2 s^-1 per cm² of applied soil.     

Assessment of metal concentrations in atmospheric particles from Burnaby Lake,British Columbia,Canada

Trace metals were assessed in atmospheric particulates at Burnaby Lake, in the greater Vancouver area of British Columbia to assess concentrations, particle size distributions and deposition rates to an urban watershed. Week-long samples were collected over a period of 18 weeks in 1995 using a 13 stage low pressure impactor (LPI). Samples were analysed using inductively coupled plasma atomic emission spectroscopy (ICP). Aluminum, boron, calcium, iron, magnesium, manganese, sodium and strontium had a similar time series pattern and particle size distribution. For these metals, maximum concentrations occurred during weeks of low precipitation and exhibited a large peak in mid June. Their particle size distribution was mostly dominated by a large peak between 1.7–18.4 μm with a secondary peak at <0.08 μm. Metal concentrations were generally one to three orders of magnitude higher than those measured in a rural location 100 km away from Burnaby Lake but similar to those measured in urban Taipei, Taiwan. Concentrations of the highly toxic metals, arsenic, cadmium and lead were within current air quality guidelines, however boron exceeded the Ontario Ministry of Environment ambient air quality standard in two of the 16 samples. Deposition velocities ranged between 0.22 and 13 cm s⁻¹ with the largest values corresponding to the coarse particle mode. Mean deposition rates ranged between 4.0 μg m⁻² d⁻¹ and 650 mg m⁻² d⁻¹. Depending on the metal, yearly loadings to the watershed ranged from 90 kg to several thousand tonnes. Calcium, aluminum, boron and magnesium had the highest metal loadings to the watershed. Manganese also had relatively high loadings, a reflection of the high traffic density in the area. The relatively high metal deposition rates indicate that metal contribution from atmospheric sources may represent a significant portion of the total metal load to the Burnaby Lake watershed.     

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) in biosolids from municipal wastewater treatment plants in China

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) along with methoxylated polybrominated diphenyl ethers (MeO-PBDEs) have been frequently identified as natural compounds in marine environment and also assumed as metabolites of PBDEs. In the present study, nine OH-PBDE, nine MeO-PBDE and 10 PBDE congeners were studied in the sewage sludge collected from 36 municipal wastewater treatment plants (WWTPs) in 27 cities of China. The results suggest that OH-PBDEs and PBDEs are ubiquitous in sewage sludge in China, however, methoxylated PBDEs were not detectable. Composition profiles of detected OH-PBDE congeners were different depending on the sampling location. ΣOH-PBDEs in WWTPs sludge ranged from 0.04 to 2.24 ng g^?1 dry weight (mean: 0.35 ng g^?1 dry weight). The total amount of the two most prominent congeners (6-OH-BDE-47 + 2′-OH-BDE-68) accounted for about 53.3–100% of the sum of all six identified congeners. A significant linear relationship was found between 6-OH-BDE-47 and 2′-OH-BDE-68. A distinct geographical distribution of ΣOH-PBDEs was observed with greater concentrations of OH-PBDEs at coastal areas than inland regions in China.     

Recreational atmospheric pollution episodes: Inhalable metalliferous particles from firework displays

The use of fireworks creates an unusual and distinctive anthropogenic atmospheric pollution event. We report on aerosol samples collected during Las Fallas in Valencia, a 6-day celebration famous for its firework displays, and add comparative data on firework- and bonfire-contaminated atmospheric aerosol samples collected from elsewhere in Spain (Barcelona, L’Alcora, and Borriana) and during the Guy Fawkes celebrations in London. Specific high-profile official firework events during Las Fallas included the afternoon Mascletà and the nightly aerial displays (especially in the climactic final 2 days of the fiesta) and were accompanied by pollution spikes in suspended particles, NO, SO₂, and the creation and dispersal of an aerosol cloud enriched in a range of metallic elements. Notable metal aerosol concentration increases recorded during Las Fallas were potassium (from 500 to 5900 ng m⁻³), aluminium (as Al₂O₃ from around 600 to 2200 ng m⁻³), titanium (from 200 to 700 ng m⁻³), magnesium (from 100 to 500 ng m⁻³), lead (from 17 to 379 ng m⁻³), barium (from 39 to 322 ng m⁻³), strontium (from 3 to 112 ng m⁻³), copper (from 12 to 71 ng m⁻³), and antimony (from 1 to 52 ng m⁻³). Firework-contaminated aerosols of similarly metalliferous composition were also identified at the other monitoring sites, although different sites show variations attributable to other sources such as bonfires and local industry. Unusual levels of the trace elements Ba, Sr and (to a lesser extent) Cu, always in proportions with Ba dominant, along with strongly enhanced K, Pb, and Sb, are identified as being particularly characteristic of firework aerosols. Although firework-related recreational pollution episodes are transient in nature, they are highly concentrated, contribute significantly to total annual metal emissions, and are on average fine enough to be easily inhaled and a health risk to susceptible individuals.     

Metal mobilization in soil by two structurally defined polyphenols

Polyphenols including tannins comprise a large percentage of plant detritus such as leaf litter, and affect soil processes including metal dynamics. We tested the effects of tannins on soil metal mobilization by determining the binding stoichiometries of two model polyphenols to Al(III) and Fe(III) using micelle-mediated separation and inductively coupled plasma optical emission spectroscopy (ICP-OES). By fitting the data to the Langmuir model we found the higher molecular weight polyphenol (oenothein B) was able to bind more metal than the smaller polyphenol (epigallocatechin gallate, EGCg). For example, oenothein B bound 9.43 mol Fe mol^?1, while EGCg bound 4.41 mol of Fe mol^?1. Using the parameters from the binding model, we applied the Langmuir model for competitive binding to predict binding for mixtures of Al(III) and Fe(III). Using the parameters from the single metal experiments and information about polyphenol sorption to soils we built a model to predict metal mobilization from soils amended with polyphenols. We tested the model with three natural soils and found that it predicted mobilization of Fe and Al with r² = 0.92 and r² = 0.88, respectively. The amount of metal that was mobilized was directly proportional to the maximum amount of metal bound to the polyphenol. The secondary parameter in each model was the amount of weak organically chelated Fe or Al that was in the soil. This study provides the first compound-specific information about how natural polyphenols interact with metals in the environment. We propose a model that is applicable to developing phytochelation agents for metal detoxification, and we discuss how tannins may play a role in metal mobilization from soils.     

Simultaneous reduction of Cr(VI) and oxidation of As(III) by Bacillus firmus TE7 isolated from tannery effluent

Hexavalent chromium [Cr(VI)] and arsenite [As(III)] are the most toxic forms of chromium and arsenic respectively, and reduction of Cr(VI) to Cr(III) and oxidation of As(III) to As(V) has great environmental implications as they affect toxicity and mobility of these toxic species. Bacillus firmus strain TE7, resistant to chromium and arsenic was isolated from tannery effluent. The strain exhibited ability to reduce Cr(VI) and oxidize As(III). It reduced 100 mg L^?1 Cr(VI) within 60 h in nutrient broth and oxidized 150 mg L^?1 As(III) within 10 h in minimal medium. It also completely reduced 15 mg L^?1 Cr(VI) and oxidized 50 mg L^?1 of As(III) simultaneously in minimal medium. To the best of our knowledge, this is the first bacterial strain showing simultaneous reduction of Cr(VI) and oxidation of As(III) and is a potential candidate for bioremediation of environments contaminated with these toxic metal species.     

The influence of light exposure,water quality and vegetation on the removal of sulfonamides and tetracyclines: A laboratory-scale study

The effect of aquatic vegetation (Spyrogira sp. and Zannichellia palustris), light exposure and water quality (secondary-treated wastewater vs. ultrapure water) on the removal efficiency of six antibiotics (sulfonamides and tetracyclines) is studied in laboratory-scale reactors. After 20 d of treatment, 3–59% of sulfonamides were eliminated in the reactors exposed to light. Removal was about 10% in unplanted reactors in darkness. The elimination of tetracycline (TC) and oxytetracycline (OTC) ranged between 83% and 97% in both planted and unplanted reactors. However, in dark unplanted reactors, OTC was largely removed (88%) while only 15% of TC was eliminated. These results suggest that TC was mainly removed by photodegradation whereas biodegradation or hydrolysis process seems to be significant processes for OTC. Sulfonamides were mainly eliminated by biodegradation or indirect photodegradation processes. Pseudo-first order kinetics removal rates ranged from 0.003 and 0.007 d^?1 for Sulfamethazine and TC in the covered control reactors to 0.13 and 0.21 d^?1 for TC and OTC in the uncovered control reactors, with half-lives from 3 to 350 d. A TC photodegradation product was tentatively identified in uncovered reactors. This study highlights the important role played by light exposure in the elimination of antibiotics in polishing ponds.     

Haloacetic acid removal by sequential zero-valent iron reduction and biologically active carbon degradation

An innovative haloacetic acid (HAA) removal process was developed. The process consisted of a zero-valent iron (Fe⁰) column followed by a biologically active carbon (BAC) column that were efficient in degrading tri- and di-HAAs, and mono- and di-HAAs, respectively. The merit of the process was demonstrated by its performance in removing trichloroacetic acid (TCAA). An empty bed contact time of 10 min achieved nearly complete removal of 1.2 μM TCAA and its subsequent products, dichloroacetic acid (DCAA) and monochloroacetic acid (MCAA). HAA removal was a result of chemical dehalogenation and biodegradation rather than physical adsorption. Preliminary kinetic analyses were conducted and the pseudo-first-order rate constants were estimated at ambient conditions for Fe⁰ reduction of TCAA and biodegradation of DCAA and MCAA by BAC. This innovative process is highly promising in removing HAAs from drinking water, swimming pool water, and domestic or industrial wastewater.     

Removal of aqueous lead by poorly-crystalline hydroxyapatites

The use of a phosphorus amendment in altering Pb to a chemically less mobile phase is a promising strategy based on minimizing ecotoxicological risk and improving time and cost efficiency. This study evaluated crystalline and poorly-crystalline hydroxyapatite sorbents on removal of aqueous Pb in response to reaction time, solution pH, and Pb concentration. Batch experiments were conducted using a commercially-available crystalline hydroxyapatite (HA), and two poorly-crystalline hydroxyapatites synthesized from gypsum waste (CHA) and incinerated ash of poultry waste (MHA). Poorly-crystalline hydroxyapatites had greater capacity for Pb removal from a solution with a wider pH range as compared to a crystalline hydroxyapatite. The maximum sorption capacity of Pb determined by the Langmuir model was 500 mg g⁻¹ for CHA, 277 mg g⁻¹ for MHA and 145 mg g⁻¹ for HA. Removal of aqueous Pb by CHA was not dependent on solution pH, with a 98.8% reduction throughout the solution pH range of 2–9, whereas aqueous Pb removal by HA and MHA was pH-dependent with less removal in the neutral solution pH. Poorly-crystalline hydroxyapatites may provide an effective alternative to existing remediation technologies for Pb-contaminated sites.     

Emission of polycyclic aromatic hydrocarbons from gasohol and ethanol vehicles

The exhaust emission of the polycyclic aromatic hydrocarbons (PAHs) considered toxic to human health were investigated on two spark ignition light duty vehicles, one being gasohol (Gasohol, in Brazil, is the generic denomination for mixtures of pure gasoline plus 20–25% of anhydrous ethyl alcohol fuel (AEAF).)-fuelled and the other a flexible-fuel vehicle fuelled with hydrated ethanol. The influence of fuel type and quality, aged lubricant oil type and use of fuel additives on the formation of these compounds was tested using standardized tests identical to US FTP-75 cycle. PAH sampling and chemical analysis followed the basic recommendations of method TO-13 (United States. Environmental Protection Agency, 1999. Compendium Method TO-13A – Determination of polycyclic Aromatic hydrocarbons (PAH) in Ambient Air Using Gas Chromatography/Mass Spectrometry (CG/MS). Center for environmental research information, Cincinnati, p. 78), with the necessary modification for this particular application.Results showed that the total PAH emission factor varied from 41.9 μg km^?1 to 612 μg km^?1 in the gasohol vehicle, and from 11.7 μg km^?1 to 27.4 μg km^?1 in the ethanol-fuelled vehicle, a significant difference in favor of the ethanol vehicle. Generally, emission of light molecular weight PAHs was predominant, while high molecular weights PAHs were not detected. In terms of benzo(a)pyrene toxicity equivalence, emission factors varied from 0.00984 μg TEQ km^?1 to 4.61 μg TEQ km^?1 for the gasohol vehicle and from 0.0117 μg TEQ km^?1 to 0.0218 μg TEQ km^?1 in the ethanol vehicle.For the gasohol vehicle, results showed that the use of fuel additive causes a significant increase in the emission of naphthalene and phenanthrene at a confidence level of 90% or higher; the use of rubber solvent on gasohol showed a reduction in the emission of naphthalene and phenanthrene at the same confidence level; the use of synthetic oil instead of mineral oil also contributed significantly to a decrease in the emission of naphthalene and fluorene. In relation to the ethanol vehicle, the same factors were tested and showed no statistically significant influence on PAH emission.     

Comparison of monometal and multimetal adsorption in Mississippi River alluvial wetland sediment: Batch and column experiments

Monometal and multimetal adsorption of selected heavy metals in a sediment from a coastal Louisiana forested swamp used for wastewater treatment was studied. Results from the batch experiments show that the maximum adsorption capacities of the metals by the sediment were in the order of Pb ≫ Hg > Cr > Cd ⩾ Cu ⩾ Zn ≫ As based on monometal adsorption isotherm, and Hg > Cr > Cu ⩾ Cd ≈ Pb ≫ As ≈ Zn based on multimetal adsorption isotherm, respectively. Batch experimental data best fit the Langmuir model rather than the Freundlich isotherms. In the column experiments, the maximum adsorption capacities of the metals were in the order of Pb ≫ Hg > Cr > Cd > Cu > Zn ≫ As in monometal conditions, and Hg ≫ Cr ≫ Pb > Cu ⩾ Zn ≈ Cd > As in multimetal conditions. The metals became more mobile in multimetal than in monometal conditions. Results from both the batch and column experiments show that competitive adsorption among metals increases the mobility of these metals. Particularly, in this study, Pb in multimetal conditions lost it adsorption capacity most significantly. In both monometal and multimetal conditions, the maximum adsorption capacity of the metals in the column experiments was higher than that in the batch experiment indicating other metal retention mechanisms rather than adsorption may be involved. Therefore, both column and batch experiments are needed for estimating retention capacities and removal efficiencies of metals in sediments.