A strategy for aromatic hydrocarbon bioremediation under anaerobic conditions and the impacts of ethanol: a microcosm study

Increased use of ethanol-blended gasoline (gasohol) and its potential release into the subsurface have spurred interest in studying the biodegradation of and interactions between ethanol and gasoline components such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) in groundwater plumes. The preferred substrate status and the high biological oxygen demand (BOD) posed by ethanol and its biodegradation products suggests that anaerobic electron acceptors (EAs) will be required to support in situ bioremediation of BTEX. To develop a strategy for aromatic hydrocarbon bioremediation and to understand the impacts of ethanol on BTEX biodegradation under strictly anaerobic conditions, a microcosm experiment was conducted using pristine aquifer sand and groundwater obtained from Canadian Forces Base Borden, Canada. The initial electron accepter pool included nitrate, sulfate and/or ferric iron. The microcosms typically contained 400 g of sediment, 600 approximately 800 ml of groundwater, and with differing EAs added, and were run under anaerobic conditions. Ethanol was added to some at concentrations of 500 and 5000 mg/L. Trends for biodegradation of aromatic hydrocarbons for the Borden aquifer material were first developed in the absence of ethanol, The results showed that indigenous microorganisms could degrade all aromatic hydrocarbons (BTEX and trimethylbenzene isomers-TMB) under nitrate- and ferric iron-combined conditions, but not under sulfate-reducing conditions. Toluene, ethylbenzene and m/p-xylene were biodegraded under denitrifying conditions. However, the persistence of benzene indicated that enhancing denitrification alone was insufficient. Both benzene and o-xylene biodegraded significantly under iron-reducing conditions, but only after denitrification had removed other aromatics. For the trimethylbenzene isomers, 1,3,5-TMB biodegradation was found under denitrifying and then iron-reducing conditions. Biodegradation of 1,2,3-TMB or 1,2,4-TMB was slower under iron-reducing conditions. This study suggests that addition of excess ferric iron combined with limited nitrate has promise for in situ bioremediation of BTEX and TMB in the Borden aquifer and possibly for other sites contaminated by hydrocarbons. This study is the first to report 1,2,3-TMB biodegradation under strictly anaerobic condition. With the addition of 500 mg/L ethanol but without EA addition, ethanol and its main intermediate, acetate, were quickly biodegraded within 41 d with methane as a major product. Ethanol initially present at 5000 mg/L without EA addition declined slowly with the persistence of unidentified volatile fatty acids, likely propionate and butyrate, but less methane. In contrast, all ethanol disappeared with repeated additions of either nitrate or ferric iron, but acetate and unidentified intermediates persisted under iron-enhanced conditions. With the addition of 500 mg/L ethanol and nitrate, only minor toluene biodegradation was observed under denitrifying conditions and only after ethanol and acetate were utilized. The higher ethanol concentration (5000 mg/L) essentially shut down BTEX biodegradation likely due to high EA demand provided by ethanol and its intermediates. The negative findings for anaerobic BTEX biodegradation in the presence of ethanol and/or its biodegradation products are in contrast to recent research reported by Da Silva et al. [Da Silva, M.L.B., Ruiz-Aguilar, G.M.L., Alvarez, P.J.J., 2005. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate. Biodegradation. 16, 105-114]. Our results suggest that the apparent conservation of high residual labile carbon as biodegradation products such as acetate makes natural attenuation of aromatics less effective, and makes subsequent addition of EAs to promote in situ BTEX biodegradation problematic.     

Fungal biofilters for toluene biofiltration: evaluation of the performance with four packing materials under different operating conditions

Packing materials play a key role in the performance of bioreactors for waste gas treatment and particularly in biofilter applications. In this work, the performance of four differently packed biofilters operated in parallel for the treatment of relatively high inlet concentration of toluene was studied. The reactors were compared for determining the suitability of coconut fiber, digested sludge compost from a waste water treatment plant, peat and pine leaves as packing materials for biofiltration of toluene. A deep characterisation of materials was carried out. Biological activity and packing capabilities related to toluene removal were determined throughout 240 days of operation under different conditions of nutrients addition and watering regime. Also, biofilters recovering after a short shutdown was investigated. Nutrient addition resulted in improved removal efficiencies (RE) and elimination capacities (EC) of biofilters reaching maximum ECs between 75 and 95 g m(-3)h(-1) of toluene. In the first 80 days, the pH decreased progressively within the reactors, causing a population change from bacteria to fungi, which were the predominant decontaminant microorganisms thereafter. All reactors were found to recover the RE rapidly after a 5 days shutdown and, in a maximum of 7 days, all reactors had been completely recuperated. These results point out that fungal biofilters are a suitable choice to treat high loads of toluene. In general, coconut fiber and compost biofilters exhibited a better performance in terms of elimination capacity and long-term stability.     

Pesticide fate in tropical wetlands of Brazil: an aquatic microcosm study under semi-field conditions

A contamination of off-site aquatic environments with pesticides has been observed in the tropics, yet only sparse information exists about pesticide fate in such ecosystems. The objective of our semi-field study was to elucidate the fate of alachlor, atrazine, chlorpyrifos, endosulfan, metolachlor, profenofos, simazine, and trifluralin in the aqueous environment of the Pantanal wetland (MT, Brazil). To this aim, water and water/sediment microcosms of two sizes (0.78 and 202 l) were installed in the outskirts of this freshwater lagoon environment and pesticide dissipation was monitored for up to 50 d after application. The physical-chemical water conditions that developed in the microcosms were reproducible among field replicates for both system sizes. Pesticide dissipation was substantially enhanced for most pesticides in small microcosms relative to the large ones (reduced DT(50) by a factor of up to 5.3). The presence of sediment in microcosms led to increased persistence of chlorpyrifos, endosulfan, and trifluralin in the test systems, while for polar pesticides (alachlor, atrazine, metolachlor, profenofos, and simazine) a lesser persistence was observed. Atrazine, simazine, metolachlor, and alachlor were identified as the most persistent pesticides in large water microcosms (DT(50) > or = 47 d); in large water/sediment systems endosulfan beta, atrazine, metolachlor, and simazine showed the slowest dissipation (DT(50) > or = 44 d). A medium-term accumulation in the sediment of tropical ecosystems can be expected for chlorpyrifos and endosulfan isomers (11-35% of applied amount still extractable at 50 d after application). We conclude that the persistence of the studied pesticides in aquatic ecosystems of the tropics is not substantially lower than during summer in temperate regions.     

Degradation of carbofuran and carbofuran-derivatives in presence of humic substances under basic conditions

The influence of humic aggregates in water solution upon the chemical stability of carbofuran (CF) and the carbofuran-derivatives, 3-hydroxy-carbofuran (HCF) and 3-keto-carbofuran (KCF), has been investigated in basic media. An inhibition upon the basic hydrolysis of 3-hydroxy-carbofuran and 3-keto-carbofuran (∼1.7 and ∼1.5-fold, respectively) was observed and it was rationalized in terms of the micellar pseudophase model. Nevertheless, non-significant effect upon the carbofuran stability was found in the presence of humic substances. These behaviors have been compared with the corresponding ones in other synthetic colloidal aggregates.     

Degradation of carbofuran and carbofuran-derivatives in presence of humic substances under basic conditions

The influence of humic aggregates in water solution upon the chemical stability of carbofuran (CF) and the carbofuran-derivatives, 3-hydroxy-carbofuran (HCF) and 3-keto-carbofuran (KCF), has been investigated in basic media. An inhibition upon the basic hydrolysis of 3-hydroxy-carbofuran and 3-keto-carbofuran (∼1.7 and ∼1.5-fold, respectively) was observed and it was rationalized in terms of the micellar pseudophase model. Nevertheless, non-significant effect upon the carbofuran stability was found in the presence of humic substances. These behaviors have been compared with the corresponding ones in other synthetic colloidal aggregates.     

The statistics of chemical trace concentrations in the steady state

The steady state probability distribution of chemical tracers in the atmosphere and in rain can be calculated from stochastic models, under explicit assumptions. We compare predictions from two such models, one based upon a linear stochastic equation in which random removal events … or storms … form a Poisson process, and the other based upon multiplicative random processes which produce a lognormal distribution. The two models predict different shapes for the resulting distributions of concentrations and fluxes of atmospheric tracers such as sulfates in ‘acid rain’. Consequently, estimates of the frequencies of extreme events, if based upon an assumed parametric form of a distribution function whose parameters are fitted by measurements of typical events, are model sensitive.To establish a preferred model for wet deposition, we have examined the statistics of sulfate deposition from the “European Network for the Study of Long Range Transport of Air Pollutants” (LRTAP), during the years 1973–1975. The shapes of the distributions of airborne sulfur species (SO₂+ SO₄²⁻), and of raincarried sulfate fluxes to the ground, are between those predicted by the two models.Our results are of operational significance to efforts directed to establishing national standards for rain quality.     

Resource competition of Cyanobacteria, Chlorococcalesa and diatoms for ammonium ions under steady and non-steady state

Cyanobacteria, Chlorococcalesa, and diatoms were investigated on competing characteristics under limited ammonium in steady and non steady state. Results showed that M. aeruginosa, S. quadricauda, and N. palea coexisted at all series of ammonium concentration in steady state. M. aeruginosa and S. quadricauda coexisted at per day, per-2-day, and per-4-day supply modes. M. aeruginosa dominated at per-8-day mode where S. quadricauda and N. palea were washed out. Monod model can predict the competing results only at quite low N concentration, while Droop model can exactly explain the results at most of N concentrations in laboratory.     

Speciation and persistence of doxycycline in the aquatic environment: Characterization in terms of steady state kinetics

The aim of the present work was to establish the kinetics for the degradation of doxycycline in the aquatic environment with a view to arriving at a kinetic model that can be used to predict the persistence of antibiotic with confidence. The degradation of doxycycline in both water and sediment phases of aquatic microcosm experiments, as well as in distilled water control experiments, was studied over a period of 90 days. An initial 21% loss due to adsorption by the sediment was observed in the microcosm experiment soon after charging. Biphasic zero-order linear rates of degradation, attributed to microbial degradation of the free and sediment or colloidal particle-adsorbed antibiotic, were observed for both water phase (2.3 × 10^?2 and 4.5 × 10^?3 μgg^?1 day^?1) and sediment phase (7.9 × 10^?3 and 1.5 × 10^?3 μgg^?1 day^?1) of the microcosm experiment. The covered distilled water control experiment exhibited a monophasic zero-order linear rate (1.9 × 10^?3 μgg^?1 day^?1) attributed to hydrolysis, while the distilled water experiment exposed to natural light exhibited biphasic liner rates attributed to a combination of hydrolysis and photolysis (2.9 × 10^?3 μgg^?1 day^?1) and to microbial degradation (9.8 × 10^?3 μgg^?1 day^?1). A kinetic model that takes into account hydrolysis, photolysis, microbial degradation as well as sorption/desorption by colloidal and sediment particles is presented to account for the observed zero-order kinetics. The implications of the observed kinetics on the persistence of doxycycline in the aquatic environment are discussed.     

Assessment of coal spontaneous combustion index gas under different oxygen concentration environment: an experimental study

Environmental Science and Pollution Research - Oxygen plays a crucial role in coal spontaneous combustion (CSC), and the magnitude of oxygen concentration determines the oxidation reaction...     

Numerical experiments and field results on the size of steady state plumes

Contaminated groundwater poses a serious risk for drinking water supplies. Under certain conditions, however, groundwater contamination remains restricted to a tolerable extent because of natural attenuation processes. We present an innovative approach to evaluate the size of these so-called steady-state plumes by 2-D and 1-D modelling in homogeneous aquifers. If longitudinal mixing is negligible, scenarios can be modelled in a simplified way using a 1-D domain vertical to the direction of flow. We analysed the sensitivity of the plume length with respect to biodegradation kinetics, flow velocity, transverse vertical dispersivity alphat, the source and aquifer geometry and reaction stoichiometry. Our findings indicate that for many readily biodegradable compounds transverse-dispersive mixing rather than reaction kinetics is the limiting factor for natural attenuation. Therefore, if alphat, aquifer and source geometry and concentrations of electron acceptors and donors are known, the length of the steady state contaminant plume can be predicted. The approach is validated under field conditions for an ammonium plume at a former landfill site in SW Germany.     

Grid lysimeter study of steady state chloride transport in two Spodosol types using TDR and wick samplers.

Solute transport in soils is affected by soil layering and soil-specific morphological properties. We studied solute transport in two sandy Spodosols: a dry Spodosol developed under oxidizing conditions of relatively deep groundwater and a wet Spodosol under periodically reducing conditions above a shallow groundwater table. The wet Spodosol is characterized by a diffuse and heterogeneous humus-B-horizon (i.e., Spodic horizon), whereas the dry Spodosol has a sharp Spodic horizon. Drainage fluxes were moderately variable with a coefficient of variation (CV) of 25% in the wet Spodosol and 17% in the dry Spodosol. Solute transport in 1-m-long and 0.8-m-diameter soil columns was investigated using spatial averages of solute concentrations measured by a network of 36 Time Domain Reflectometry (TDR) probes. In the dry Spodosol, solute transport evolves from stochastic-convective to convective-dispersive at a depth of 0.25 m, coinciding with the depth of the Spodic horizon. Chloride breakthrough at the bottom of the soil columns was adequately well predicted by a convection-dispersion model. In the wet Spodosol, solute transport was heterogeneous over the entire depth of the column. Chloride breakthrough at 1 m depth was predicted best using a stochastic-convective transport model. The TDR sampling volume of 36 probes was too small to capture the heterogeneous flow and concomitant transport in the wet Spodosol.     

Comparison of experimental ponds for the treatment of dye wastewater under controlled and semi-natural conditions

This study compares the performance of simulated shallow ponds vegetated with Lemna minor L. under controlled and semi-natural conditions for the treatment of simulated wastewater containing textile dyes. The objectives were to assess the water quality outflow parameters, the potential of L. minor concerning the removal of chemical oxygen demand (COD) and four azo dyes (Acid blue 113, reactive blue 198, Direct Orange 46 and Basic Red 46) and the plants’ growth rate. Findings show that all mean outflow values of COD, total dissolved solids (TDS) and electrical conductivity (EC) were significantly (p < 0.05) lower within the outdoor compared to the indoor experiment except the dissolved oxygen (DO). The COD removal was low for both experiments. The outflow TDS values were acceptable for all ponds. The pond systems were able to reduce only BR46 significantly (p < 0.05) for the tested boundary conditions. Removals under laboratory conditions were better than those for semi-natural environments, indicating the suitability of operating the pond system as a polishing step in warmer regions. The mean outflow values of zinc and copper were below the thresholds set for drinking and irrigation waters and acceptable for L. minor. The dyes inhibited the growth of the L. minor.     

A computational study of particulate emissions from an open pit quarry under neutral atmospheric conditions

The extraction of minerals from surface mines and quarries can produce significant fugitive dust emissions as a result of site activities such as blasting, road haulage, loading, crushing and stockpiling. If uncontrolled, these emissions can present serious environmental, health, safety and operational issues impacting both site personnel and the wider community.The dispersion of pollutant emissions within the atmosphere is principally determined by the background wind systems characterized by the atmospheric boundary layer (ABL). This paper presents an overview of the construction and solution of a computational fluid dynamics (CFD) model to replicate the development of the internal ventilation regime within a surface quarry excavation due to the presence of a neutral ABL above this excavation. This model was then used to study the dispersion and deposition of fugitive mineral dust particles generated during rock blasting operations. The paths of the mineral particles were modelled using Lagrangian particle tracking. Particles of four size fractions were released from five blast locations for eight different wind directions.The study concluded that dependent on the location of the bench blast within the quarry and the direction of the wind, a mass fraction of between 0.3 and 0.6 of the emitted mineral particles was retained within the quarry. The retention was largest when the distance from the blast location to the downwind pit boundary was greatest.     

Influence of the initial state of carbon nanotubes on their colloidal stability under natural conditions

The colloidal stability of dry and suspended carbon nanotubes (CNTs) in the presence of amphiphilic compounds (i.e. natural organic matter or surfactants) at environmentally realistic concentrations was investigated over several days. The suspensions were analyzed for CNT concentration (UV-vis spectroscopy), particle size (nanoparticle tracking analysis), and CNT length and dispersion quality (TEM). When added in dry form, around 1% of the added CNTs remained suspended. Pre-dispersion in organic solvent or anionic detergent stabilized up to 65% of the added CNTs after 20 days of mild shaking and 5 days of settling. The initial state of the CNTs (dry vs. suspended) and the medium composition hence are critical determinants for the partitioning of CNTs between sediment and the water column. TEM analysis revealed that single suspended CNTs were present in all suspensions and that shaking and settling resulted in a fractionation of the CNTs with shorter CNTs remaining predominantly in suspension.     

Modelling of physical and reactive processes during biodegradation of a hydrocarbon plume under transient groundwater flow conditions

Numerical experiments of non-reactive and reactive transport were carried out to quantify the influence of a seasonally varying, transient flow field on transport and natural attenuation at a hydrocarbon-contaminated field site. Different numerical schemes for solving advective transport were compared to assess their capability to model low transversal dispersivities in transient flow fields. For the field site, it is shown that vertical plume spreading is largely inhibited, particularly if sorption is taken into account. For the reactive simulations, a biodegradation reaction module for the geochemical transport model PHT3D was developed. Results of the reactive transport simulations show that under the site-specific conditions the temporal variations in groundwater flow do, to a modest extent, affect average biodegradation rates and average total (dissolved) contaminant mass in the aquifer. The model simulations demonstrate that the seasonal variability in groundwater flow only results in significantly enhanced biodegradation rates when a differential sorption of electron donor (toluene) and electron acceptor (sulfate) is assumed.     

Secondary organic aerosol formation from cyclohexene ozonolysis in the presence of water vapor and dissolved salts

A series of 90 experiments were conducted in the UC Riverside/CE-CERT environmental chamber to evaluate the impact of water vapor and dissolved salts on secondary organic aerosol formation for cyclohexene ozonolysis. Water vapor (low – 30 ± 2% RH, medium – 46 ± 2% RH, high – 63 ± 2% RH) was found to directly participate in the atmospheric chemistry altering the composition of the condensing species, thus increasing total organic aerosol formation by ～22% as compared to the system under dry (<0.1% RH) conditions. Hygroscopicity measurements also indicate that the organic aerosol composition is altered in the presence of gaseous water. These results are consistent with water vapor reacting with the crigee intermediate in the gas phase resulting in increased aldehyde formation. The addition of dissolved salts ((NH₄)₂SO₄, NH₄HSO₄, CaCl₂, NaCl) had minimal effect; only the (NH₄)₂SO₄ and NaCl were found to significantly impact the system with ～10% increase in total organic aerosol formation. These results indicate that the organics may be partitioning to an outer organic shell as opposed to into the aqueous salt. Hygroscopicity measurements indicate that the addition of salts does not alter the aerosol composition for the dry or water vapor system.     

UASB反应器对芳香族化合物反硝化降解特性研究

以苯、联苯和萘为模型化合物,研究了上流式厌氧污泥床反应器(UASB)在反硝化连续流运行条件下对含上述污染物废水的处理效果,并以葡萄糖为补充碳源,考察了COD/NO^-₃-N(简称C/N)比对有机物反硝化降解特性的影响。研究结果表明,当进水COD浓度约为900 mg/L,苯、联苯和萘总浓度约为60 mg/L,NO^-₃-N为20～60 mg/L时,UASB反应器能够在硝酸盐还原条件下稳定去除废水中有机污染物,其中COD平均去除率可达到85%,苯、萘和联苯平均去除率分别为90%、81%和71%。3种芳香烃反硝化降解速率顺序为苯>萘>联苯。 C/N比对苯的降解影响不十分显著,在C/N为5～30范围内,苯的去除率稳定在87%～92%;萘和联苯去除率受C/N影响较大,在C/N比为15时萘和联苯的去除率均达到最大,分别为82%和77%。     

Constructed treatment wetland: a study of eight plant species under saline conditions

A series of investigations was conducted to evaluate the feasibility of using constructed treatment wetlands to remove pollutants from saline wastewater. Eight emergent plants; cattail, sedge, water grass, Asia crabgrass, salt meadow cordgrass, kallar grass, vetiver grass and Amazon, were planted in experimental plots and fed with municipal wastewater that was spiked with sodium chloride (NaCl) to simulate a saline concentration of approximately 14-16 mScm-1. All macrophytes were found tolerant under the tested conditions except Amazon and vetiver grass. Nutrient assimilation of salt tolerant species was in the range of 0.006-0.061 and 0.0002-0.0024 gm-2d-1 for nitrogen and phosphorus, respectively. Treatment performances of planted units were found to be 72.4-78.9% for BOD5, 43.2-56.0% for SS, 67.4-76.5% for NH3-N and 28.9-44.9% for TP. The most satisfactory plant growth and nitrogen assimilation were found for cattail (Typha angustifolia) though the plant growth was limited, whereas Asia crabgrass (Digitaria bicornis) was superior for BOD5 removal. Both were evaluated again in a continuous flow constructed wetland system receiving saline feed processing wastewater. A high removal rate regularly occurred in long-term operating conditions. The reduction in BOD5, SS, NH3-N and TP was in the range of 44.4-67.9%, 41.4-70.4%, 18.0-65.3% and 12.2-40.5%, respectively. Asia crabgrass often provided higher removal especially for BOD5 and SS removal. Nutrient enriched wastewater promoted flourishing growth of algae and plankton in the surface flow system, which tended to reduce treatment performance.     

Uptake and elimination,and effect of estrogen-like contaminants in estuarine copepods: an experimental study

Background, aim, and scope  

In recent years, anthropogenic chemicals which can disrupt the hormonal systems of both humans and wildlife have been raised to a major cause of concern. The aim of the present work was to determine the bioconcentration factors of the two major alkylphenols (AP) of the Seine Estuary [4-nonylphenol (4 NP) and nonylphenol acetic acid (NP1EC)] and of the synthetic estrogen, estrogen ethinylestradiol (EE2), in Eurytemora affinis after exposure in a continuous flow-through system under environmental realistic conditions. Moreover, the elimination of these compounds in copepods from the Seine Estuary has been investigated by measuring concentrations after 1 week in clean water in comparison to background levels.