Natural Attenuation Processes Research Articles

Impact of the wastewater-mixing zone on attenuation of pharmaceuticals in natural waters: Implications for an impact zone inclusive environmental risk assessment

The direct discharge of untreated wastewater has been identified as an important source of environmental contamination by active pharmaceutical ingredients and other ‘down-the-drain’ chemicals in developing countries. It necessitates the development of an environmental risk assessment approach for the resulting impact zone. This study was designed to investigate the impact of low level of dilution (<10) on the natural attenuation processes of distribution and degradation within the impact zone. Dilution of the untreated wastewater resulted in increased desorption and corresponding environmental concentrations. The presence/absence of the microbial population in the batches affected the degree of sorption depending on the compound charge (i.e. positive or negative), highlighting an experimental technical bias. The degradation half-lives of acebutolol and diclofenac increased with increasing dilution and resulted in higher environmental persistence. The modelling of the biochemical oxygen demand (BOD) allowed an estimate of the temporal end boundary of the impact zone to be predicted as 24h. Therefore, it was concluded that most of the investigated compounds would persist beyond the end of the impact zone as defined by the return to environmental BOD concentrations. It is proposed that, within environmental risk assessment protocols, the impact zone should be considered as a semi-natural wastewater treatment area in such a way to allow the estimate of environmental concentrations of pharmaceuticals beyond its end.

Environmental Fate of Petroleum Hydrocarbons in Soil: Review of Multiphase Transport, Mass Transfer, and Natural Attenuation Processes

The increasing use of petroleum-derived fuels over the last few decades has subsequently augmented the risk of spills in the environment. Soil pollution with petroleum hydrocarbons (principally caused by leaks in pipelines and underground storage tanks) is one of the major sources of soil degradation. Once in soil, fuel hydrocarbons suffer from a wide variety of multiphase processes including transport (advection, diffusion, and dispersion) among and within phases (aqueous and non-aqueous liquid, gas, and soil solids), mass transfer among phases (volatilization, sorption, and solution), and other natural attenuation processes, such as biodegradation and plant uptake and metabolism. This review identifies and describes the major processes occurring in soil that have a significant influence on the environmental fate of petroleum hydrocarbons. The definition of the processes involved in pollutant migration and distribution in soil and the formulation of adequate equations using accurate parameters (e.g., diffusion coefficients, velocity of advective flows, and mass transfer coefficients) will allow prediction of the final fate of soil pollutants. In addition to transport and mass transfer processes, which are more widely studied, the incorporation of attenuation mechanisms driven by microorganisms and plants is essential to predict the final concentration of the pollutants in the whole multiphase scenario. This work underlines the importance of the determination of accurate parameters through the performance of laboratory and/or field-scale experiments to develop precise pollutant migration models.

Impact of nanoparticles on transcriptional regulation of catabolic genes of petroleum hydrocarbon-degrading bacteria in contaminated soil microcosms.

This study was conducted to determine what effects nanoparticles (NPs) like TiO2 , ZnO, and Ag may pose on natural attenuation processes of petroleum hydrocarbons in contaminated soils. The solid NPs used were identified using x-ray diffraction technique and their average size was certified as 18.2, 16.9, and 18.3 nm for Ag-NPs, ZnO-NPs, and TiO2 -NPs, respectively. NPs in soil microcosms behave differently where it was dissolved as in case of Ag-NPs, partially dissolved as in ZnO-NPs or changed into other crystalline phase as in TiO2 -NPs. In this investigation, catabolic gene encoding catechol 2,3 dioxygenase (C23DO) was selected specifically as biomarker for monitoring hydrocarbon biodegradation potential by measuring its transcripts by RT-qPCR. TiO2 -NPs amended microcosms showed almost no change in C23DO expression profile or bacterial community which were dominated by Bacillus sp., Mycobacterium sp., Microbacterium sp., Clostridium sp., beside uncultured bacteria, including uncultured proteobacteria, Thauera sp. and Clostridia. XRD pattern suggested that TiO2 -NPs in microcosms were changed into other non-inhibitory crystalline phase, consequently, showing the maximum degradation profile for most low molecular weight oil fractions and partially for the high molecular weight ones. Increasing ZnO-NPs concentration in microcosms resulted in a reduction in the expression of C23DO with a concomitant slight deteriorative effect on bacterial populations ending up with elimination of Clostridium sp., Thauera sp., and uncultured proteobacteria. The oil-degradation efficiency was reduced compared to TiO2 -NPs amended microcosms. In microcosms, Ag-NPs were not detected in the crystalline form but were available in the ionic form that inhibited most bacterial populations and resulted in a limited degradation profile of oil, specifically the low molecular weight fractions. Ag-NPs amended microcosms showed a significant reduction (80%) in C23DO gene expression and a detrimental effect on bacterial populations including key players like Mycobacterium sp., Microbacterium sp., and Thauera sp. involved in the biodegradation of petroleum hydrocarbons.

Degradation of 4-bromophenol by Ochrobactrum sp. HI1 isolated from desert soil: pathway and isotope effects.

Anthropogenic activities have introduced elevated levels of brominated phenols to the environment. These compounds are associated with toxic and endocrine effects, and their environmental fate is of interest. An aerobic strain Ochrobactrum sp. HI1 was isolated from soils in the vicinity of a bromophenol production plant and tested for its ability to degrade 4-bromophenol (4-BP). A ring hydroxylation pathway of degradation was proposed, using the evidence from degradation intermediates analysis and multi-element (C, Br, H) compound-specific isotope analysis. Benzenetriol and 4-bromocatechol were detected during degradation of 4-bromophenol. Degradation resulted in a normal carbon isotope effect (εC = -1.11 ± 0.09‰), and in insignificant bromine and hydrogen isotope fractionation. The dual C-Br isotope trend for ring hydroxylation obtained in the present study differs from the trends expected for reductive debromination or photolysis. Thus, the isotope data reported herein can be applied in future field studies to delineate aerobic biodegradation processes and differentiate them from other natural attenuation processes.

Subsurface landfill leachate contamination affects microbial metabolic potential and gene expression in the Banisveld aquifer.

Microbial communities in groundwater ecosystems can develop the capacity to degrade complex mixtures of chemicals resulting from pollution by landfill leachate. Monitoring this natural attenuation requires insight into the metabolic potential and activity of microbial communities. We contrasted the metagenomes and metatranscriptomes from a leachate-polluted aquifer downstream of the Banisveld (the Netherlands) landfill with uncontaminated groundwater, which revealed changes in microbial genomic content and activity. Banisveld landfill leachate contains mono-aromatic hydrocarbons and the assessment of natural attenuation of these compounds in the aquifer had been a focal point of research. In the contaminated groundwater, active microbial functions were the ones involved in degradation of complex carbon substrates and organic pollutants. We found that benzylsuccinate synthase genes-involved in the catabolism of toluene-were highly expressed close to the source of contamination, confirming the ongoing natural attenuation of organic mono-aromatic hydrocarbon pollution in this aquifer. Additionally, metatranscriptomes were indicative of phosphorus limitation that can constrain total microbial activity and agree with the low phosphate concentrations (<0.4 μmol/L) in this aquifer. Through the application of metagenomics and metatranscriptomics, we were able to determine functional potential and expression patterns to assess the natural attenuation processes and constraints on microbial communities.

Unravelling long-term source removal effects and chlorinated methanes natural attenuation processes by C and Cl stable isotopic patterns at a complex field site

The effects of contaminant sources removal in 2005 (i.e. barrels, tank, pit and wastewater pipe sources) on carbon tetrachloride (CT) and chloroform (CF) concentration in groundwater were assessed at several areas of a fractured multi-contaminant aquifer (Òdena, Spain) over a long-term period (2010–2014). Changes in redox conditions, in these chlorinated methanes (CMs) concentration and in their carbon isotopic compositions (δ13C) were monitored in multilevel wells. δ13C values from these wells were compared to those obtained from sources (barrels, tank and pit before their removal, 2002–2005) and to commercial solvents values in literature. Additionally, CMs natural attenuation processes were identified by C-Cl isotope slopes (Λ).Analyses revealed the downstream migration of the pollutant focus and an efficient removal of DNAPLs in the pit source's influence area. However, the removal of the contaminated soil from former tank and wastewater pipe was incomplete as leaching from unsaturated zone was proved, evidencing these areas are still active sources. Nevertheless, significant CMs degradation was detected close to all sources and Λ values pointed to different reactions. For CT in the tank area, Λ value fitted with hydrogenolysis pathway although other possible reduction processes were also uncovered. Near the wastewater pipe area, CT thiolytic reduction combined with hydrogenolysis was derived. The highest CT degradation extent accounted for these areas was 72 ± 11% and 84 ± 6%, respectively. For CF, the Λ value in the pit source's area was consistent with oxidation and/or with transport of CF affected by alkaline hydrolysis from upstream interception trenches. In contrast, isotope data evidenced CF reduction in the tank and wastewater pipe influence areas, although the observed Λ slightly deviates from the reference values, likely due to the continuous leaching of CF degraded in the non-saturated zone by a mechanism different from reduction.

A study of the 46-year-old Arrow oil spill: Persistence of oil residues and variability in oil contamination along Chedabucto Bay, Nova Scotia, Canada

Abstract The occurrence, spatial distribution and source of petroleum-related hydrocarbons, and the degree of weathering of Arrow oil residues persisting on the shoreline of Chedabucto Bay, Nova Scotia, were assessed. The hydrocarbons assessed included total petroleum hydrocarbons (TPH), n-alkanes from n-C9 to n-C40, petroleum biomarkers like terpanes, hopanes and steranes, non-alkylated polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologues (APAHs). Trapped Arrow oil in the sunken tanker has not experienced any marked weathering. The collected environmental samples could be classified into three groups. Group 1 samples were oil free identified by low TPH, highly resolved fractions, a predominantly biogenic source of n-alkanes, and trace amounts of petroleum biomarkers probably from the historical (1970) oil spill. Group 2 samples had higher TPH and the other targets than Group 1 samples. The mixed petrogenic and terrestrial plant inputs were the source of n-alkanes, while the pattern of APAHs indicated that their source varied from site to site, being either recently released petroleum or Arrow oil residues. Group 3 samples mainly contained oil residues from Arrow oil spill, having very high levels of TPH, APAHs and biomarkers; however, most samples were free of n-alkanes. Group 3 samples were mostly found on the southern shoreline of Chedabucto Bay, especially in the upper to middle intertidal zone of the shorelines characterized by mixed pebble/cobble/boulders. The extent of weathering of n-alkanes and APAHs showed no relation to each other, although n-alkanes were depleted more fully than APAHs for most of the oil residues. Thus, various natural attenuation processes, especially for microbial degradation, have contributed to the aging of these oil residues. The degree of weathering varied with different environmental conditions.

Biogeochemical changes at the sediment\u2013water interface during redox transitions in an acidic reservoir: exchange of protons, acidity and electron donors and acceptors

Redox transitions induced by seasonal changes in water column O2 concentration can have important effects on solutes exchange across the sediment–water interface in systems polluted with acid mine drainage (AMD), thus influencing natural attenuation and bioremediation processes. The effect of such transitions was studied in a mesocosm experiment with water and sediment cores from an acidic reservoir (El Sancho, SW Spain). Rates of aerobic organic matter mineralization and oxidation of reduced inorganic compounds increased under oxic conditions (OX). Anaerobic process, like Fe(III) and sulfate reduction, also increased due to higher O2 availability and penetration depth in the sediment, resulting in higher regeneration rates of their corresponding anaerobic e− acceptors. The contribution of the different processes to oxygen uptake changed considerably over time. pH decreased due to the precipitation of schwertmannite and the release of H+ from the sediment, favouring the dissolution of Al-hydroxides and hydroxysulfates at the sediment surface. The increase in dissolved Al was the main contributor to water column acidity during OX. Changes in organic matter degradation rates and co-precipitation and dissolution of dissolved organic carbon and nitrogen with redox-sensitive Fe(III) compounds affected considerably C and N cycling at the sediment–water interface during redox transitions. The release of NO2− and NO3− during the hypoxic period could be attributed to ammonium oxidation coupled to ferric iron reduction (Feammox). Considering the multiple effects of redox transitions at the sediment–water interface is critical for the successful outcome of natural attenuation and bioremediation of AMD impacted aquatic environments.

Extent of natural attenuation of chlorinated ethenes at a contaminated site in Denmark

Chlorinated solvents contaminated soils and aquifers are a widespread problem in industrialized countries and many require clean-up due to the risk of contaminant flow into groundwater systems. Clean-up is costly and often invasive, thus there is high interest in stimulating natural attenuation processes. For this, first an assessment of the type and extent of natural attenuation present at the site is required. Here, we present chemical, isotopic and microbial analyses of waters collected at a chlorinated ethene contaminated site in Denmark to give insights into natural attenuation processes. The data gives indication of complete reductive dechlorination by microbial communities but their extent varies greatly across short distances and between the different geological layers. The data further indicates that overall, chlorinated ethene degradation through natural attenuation is small at this site but near surface degradation due to aerobic co-metabolism or abiotic geochemical reduction could potentially play a role.

Mobility and natural attenuation of metals and arsenic in acidic waters of the drainage system of Timok River from Bor copper mines (Serbia) to Danube River.

Bor, Krivelj, and Bela Rivers belong to the watershed of Timok River, which is a tributary of transboundary Danube River. These rivers receive metal-rich acidic wastewater from metallurgical facilities and acid mine drainage (AMD) from mine wastes around Bor copper mines. The aim of this study was to determine the mobility and natural attenuation of metals and arsenic in rivers from Bor copper mines to Danube River during the year 2015. The results showed that metallurgical facilities had the largest impact on Bor River by discharging about 400t of Cu per year through highly acidic wastewater (pH = 2.6). The highest measured concentrations of Cu in river water and sediments were 40mgL-1 and 1.6%, respectively. Dissolution of calcite from limestone bedrock and a high concentration of bicarbonate ions in natural river water (about 250mgL-1) enhanced the neutralization of acidic river water and subsequent chemical precipitation of metals and arsenic. Decreases in the concentrations of Al, Fe, Cu, As, and Pb in river water were mainly due to precipitation on the river bed. On the other hand, dilution played an important role in the decreases in concentrations of Mn, Ni, Zn, and Cd. Chemically precipitated materials and flotation tailings containing Fe-rich minerals (fayalite, magnetite, and pyrite) were transported toward Danube River during the periods of high discharge. This study showed that processes of natural attenuation in catchments with limestone bedrock play an important role in reducing concentrations of metals and arsenic in AMD-bearing river water.

Combining in vitro reporter gene bioassays with chemical analysis to assess changes in the water quality along the Ammer River, Southwestern Germany

BackgroundRivers receive water and associated organic micropollutants from their entire catchment, including from urban, agricultural and natural sources, and constitute an important environmental component for catalyzing pollutant turnover. Environmental removal processes were extensively investigated under laboratory conditions in the past but there is still a lack of information on how organic micropollutants attenuate on the catchment scale. The aim of this study was to describe the chemical and toxicological profile of a 4th order river and to characterize in-stream processes. We propose indicator chemicals and indicator in vitro bioassays as screening methods to evaluate micropollutant input and transport and transformation processes of the chemical burden in a river. Carbamazepine and sulfamethoxazole were selected as indicators for dilution processes and the moderately degradable chemicals tramadol and sotalol as indicators for potential in-stream attenuation processes. The battery of bioassays covers seven environmentally relevant modes of action, namely estrogenicity, glucocorticogenic activity, androgenicity progestagenic activity and oxidative stress response, as well as activation of the peroxisome proliferator-activated receptor and the aryl hydrocarbon receptor, using the GeneBLAzer test battery and the AhR-CALUX and AREc32 assays.ResultsBoth approaches, targeted chemical analysis and in vitro bioassays, identified a wastewater treatment plant (WWTP) as a major input source of organic micropollutants that dominantly influenced the water quality of the river. Downstream of the WWTP the amount of detected chemicals and biological effects decreased along the river flow. The organic indicator chemicals of known degradability uncovered dilution and potential loss processes in certain river stretches. The average cytotoxic potency of the river water decreased in a similar fashion as compounds of medium degradability such as the pharmaceutical sotalol.ConclusionsThis study showed that the indicator chemical/indicator bioassay approach is suitable for identifying input sources of a mixture of organic micropollutants and to trace changes in the water quality along small rivers. This method forms the necessary basis for evaluating the natural attenuation processes of organic micropollutants on a catchment scale, especially when combined with enhanced sampling strategies in future studies.

The past and prognosis of mining cessation impact on river sediment pollution

PurposeRemediation of mine sites is often aimed at reduction of river pollution after cessation of mining activity. However, the effects of these works overlap natural attenuation processes and their efficiency cannot be recognized well without detailed studies of the fluvial environment. The aim of the study is to predict changes of channel sediment pollution in rivers affected by mine sites after their rehabilitation, planned after mining cessation.Materials and methodsThis study utilizes data on sediment pollution in three rivers polluted by lead-zinc mining, sampled over a time span of over 20 years in southern Poland. The former and the present pollution levels have been compared between the Biała Przemsza and Sztoła Rivers continuously influenced by mine waters and the Chechło River where mining has ceased. The observed changes in sediment pollution in the three catchments have been interpreted in terms of the impact of mining cessation on sediment pollution and the observed rate of the pollution changes in the past, reconstructed also from reservoir sediments.Results and discussionIn the drainage basins of the Chechło River, a mine has been closed and the rapid drop in metal concentrations in channel, and reservoir sediments was observed within a few years. In the other two drainage basins where lead-zinc mines still operate, the metal concentrations remained at the same level. Based on the similar catchment and pollution characteristics, a drop in metal concentration in these two rivers is expected soon after ore exhaustion. Nonetheless, considering the large contamination of soils and overbank sediments in the three drainage basins due to a long mining history, the drop will be followed by a very long period when their concentrations are raised above a permissible level.ConclusionsThe study has shown that the natural fluvial attenuation processes can decrease heavy metal concentrations in channels cut in fine-grained alluvia within a few years after mine closure by one order of magnitude but the rate of the decrease depends on the frequency and magnitude of floods which will take place after mining cessation. Efforts made to mitigate pollution at mine sites may not be as efficient as fluvial processes to rapidly decrease channel sediment pollution below permissible levels.

Processes of distribution of pharmaceuticals in surface freshwaters: implications for risk assessment

The global consumption and production of pharmaceuticals is increasing concomitantly with concern regarding their environmental fate and effects. Active pharmaceutical ingredients are mainly released into the aquatic environment through wastewater effluent discharge. Once in the environment, pharmaceuticals can undergo processes of natural attenuation, i.e. dilution, sorption, transformation, depending on physico-chemical properties of the compound, such as water solubility, lipophilicity, vapour pressure, and environmental conditions, such as pH, temperature and ionic strength. A major natural attenuation process is the sorption on dissolved organic matter, colloids, suspended solids and sediments, which in turn control pharmaceuticals distribution, residence time and persistence in aquatic systems. Here we review studies of sorption capacity of natural sorbents to pharmaceuticals. These report on the importance of several environmental and sorbent-specific properties, such as the composition, quality, and amount of the sorbent, and the environmental pH, which determines the speciation of both the sorbent and compound. The importance of accounting for distribution processes on freshwater sorbents for any determination of environmental concentrations of pharmaceuticals is apparent, while the reliability of surrogate standards for measuring dissolved organic matter (DOM) distribution is evaluated in the context of the need for robust environmental risk assessment protocols.

Deactivation of wastewater-derived N-nitrosodimethylamine precursors with chlorine dioxide oxidation and the effect of pH

In this study, the effect of chlorine dioxide (ClO2) oxidation on the deactivation of wastewater (WW)-derived N-nitrosodimethylamine (NDMA) precursors was investigated under various conditions (i.e., ClO2 application pH, dose and contact time). At pH 6.0, decreases in NDMA formation potentials (FPs) or occurrences (under uniform formation conditions [UFC]) were relatively low (<25%) with ClO2 oxidation regardless of WW-impact. A negative removal was also observed after ClO2 oxidation in some of the non-impacted waters. However, NDMA FP removals were significant (up to ~85%) under the same oxidation conditions in WW-impacted waters at pH 7.8. This indicates that the majority of WW-derived NDMA precursors can be deactivated with ClO2 oxidation above neutral pH. This was attributed to the better oxidative reaction of ClO2 with amines that have lone pair electrons to be shared at higher oxidation pH conditions. In addition, relatively short oxidation periods with ClO2 (i.e., ≤10 min) or low Ct (concentration × time, ~10 mg ∗ min/L) values were sufficient for the deactivation of WW-derived NDMA precursors. ClO2 oxidation was effective in freshly WW-impacted waters. Natural attenuation processes (e.g., sorption, biodegradation, etc.) can change the reactivity of WW-derived NDMA precursors for oxidation with ClO2. The effect of ClO2 on the removal of THM precursors was low (<25%) and independent of oxidation conditions. Given the low formation of regulated THMs and HAAs, ClO2 oxidation presents a viable option for the simultaneous control of NDMA and regulated DBP formation during water treatment, especially for utilities treating WW-impacted water sources.

Common Hydraulic Fracturing Fluid Additives Alter the Structure and Function of Anaerobic Microbial Communities.

The development of unconventional oil and gas (UOG) resources results in the production of large volumes of wastewater containing a complex mixture of hydraulic fracturing chemical additives and components from the formation. The release of these wastewaters into the environment poses potential risks that are poorly understood. Microbial communities in stream sediments form the base of the food chain and may serve as sentinels for changes in stream health. Iron-reducing organisms have been shown to play a role in the biodegradation of a wide range of organic compounds, and so to evaluate their response to UOG wastewater, we enriched anaerobic microbial communities from sediments collected upstream (background) and downstream (impacted) of an UOG wastewater injection disposal facility in the presence of hydraulic fracturing fluid (HFF) additives: guar gum, ethylene glycol, and two biocides, 2,2-dibromo-3-nitrilopropionamide (DBNPA) and bronopol (C3H6BrNO4). Iron reduction was significantly inhibited early in the incubations with the addition of biocides, whereas amendment with guar gum and ethylene glycol stimulated iron reduction relative to levels in the unamended controls. Changes in the microbial community structure were observed across all treatments, indicating the potential for even small amounts of UOG wastewater components to influence natural microbial processes. The microbial community structure differed between enrichments with background and impacted sediments, suggesting that impacted sediments may have been preconditioned by exposure to wastewater. These experiments demonstrated the potential for biocides to significantly decrease iron reduction rates immediately following a spill and demonstrated how microbial communities previously exposed to UOG wastewater may be more resilient to additional spills.IMPORTANCE Organic components of UOG wastewater can alter microbial communities and biogeochemical processes, which could alter the rates of essential natural attenuation processes. These findings provide new insights into microbial responses following a release of UOG wastewaters and are critical for identifying strategies for the remediation and natural attenuation of impacted environments.

Contribution of biotic and abiotic factors in the natural attenuation of sulfamethoxazole: A path analysis approach

Sulfamethoxazole (SMX) is a sulfonamide antibiotic, widely used as curative and preventive drug for human, animal, and aquaculture bacterial infections. Its residues have been ubiquitously detected in the surface waters and sediments. In the present study, SMX dissipation and kinetics was studied in the natural water samples from Jiulong River under simulated complex natural conditions as well as conditions to mimic various biotic and abiotic environmental conditions in isolation. Structural equation modeling (SEM) by employing partial least square technique in path coefficient analysis was used to investigate the direct and indirect contributions of different environmental factors in the natural attenuation of SMX. The model explained 81% of the variability in natural attenuation as a dependent variable under the influence of sole effects of direct photo-degradation, indirect photo-degradation, hydrolysis, microbial degradation and bacterial degradation. The results of SEM suggested that the direct and indirect photo-degradation were the major pathways in the SMX natural attenuation. However, other biotic and abiotic factors also play a mediatory role during the natural attenuation and other processes. Furthermore, the potential transformation products of SMX were identified and their toxicity was evaluated.

Fluorinated waste and firefighting activities: biodegradation of hydrocarbons from petrochemical refinery soil co-contaminated with halogenated foams.

Perfluorinated compounds, including fluorotelomers, are important constituents of firefighting foams to extinguish fuel fires in the petrochemical industry, airports, and at fire-training sites. In this study, we monitored the biodegradation process in a co-contamination scenario with monoaromatic hydrocarbons commonly found in fuels (benzene, toluene) and fluorotelomers. The CO2 production rates were evaluated by a factorial design taking into account the effect of seasonality at in situ natural attenuation processes. Headspace analysis by gas chromatography with a thermal conductivity detector (GC-TCD) was applied to detect CO2 production, whereas monoaromatics were analyzed by gas chromatography coupled to mass spectrometry (GC-MS). According to our results, seasonality had a detectable effect during summer, yielding different CO2 production rates. Higher temperatures increased CO2 production rate, while higher concentrations of fluorotelomer inhibited the biodegradation process. On average, benzene and toluene were depleted 17.5days earlier in control assays without fluorotelomers. Toluene removal efficiency was also notably higher than benzene. The noticeable decrease in degradation rates of monoaromatics was caused by perfluorinated compounds that are possibly linked to metabolic inhibition mechanisms. Fluorotelomer diminished catabolism in all of our batch cultures. In addition to this, an alternative production of by-products could be detected. Thus, we propose that transient components of the benzene and toluene degradation may be differentially formed, causing the benzene, toluene, and perfluorinated co-contaminations to go through switched metabolic stages under the presence of fluoride in a contamination scenario.

Ethanol content in different gasohol blend spills influences the decision-making on remediation technologies

Gasohol blend spills with variable ethanol content exert different electron acceptor demands in groundwater and the distinct dynamics undergone by these blends underscores the need for field-based information to aid decision-making on suitable remediation technologies for each gasohol blend spill. In this study, a comparison of two gasohol releases (E10 (10:90 ethanol and gasoline, v/v) and E25 (25:75 ethanol and gasoline, v/v) under monitored natural attenuation (MNA) and nitrate biostimulation, respectively) was conducted to assess the most effective remediation strategy for each gasohol release. Microbial communities were assessed to support geochemical data as well as to enable the characterization of important population shifts that evolve during biodegradation processes in E25 and E10 field experiments. Results revealed that natural attenuation processes sufficiently supported ethanol and BTEX compounds biodegradation in E10 release, due to the lower biochemical oxygen demand they exert relative to E25 blend. In E25 release, nitrate reduction was largely responsible for BTEX and ethanol biodegradation, as intended. First-order decay constants demonstrated that ethanol degradation rates were similar (p < 0.05) for both remediation technologies (2.05 ± 0.15 and 2.22 ± 0.23, for E25 and E10, respectively) whilst BTEX compounds exhibited different degradation rates (p > 0.05) that were higher for the experiment under MNA (0.33 ± 0.06 and 0.43 ± 0.03, for E25 and E10, respectively). Therefore, ethanol content in different gasohol blends can influence the decision-making on the most suitable remediation technology, as MNA processes can be applied for the remediation of gasohol blends with lower ethanol content (i.e., 10% v/v), once the aquifer geochemical conditions provide a sufficient electron acceptor pool. To the best of our knowledge, this is the first field study to monitor two long-term gasohol releases over various time scales in order to assess feasible remediation technologies for each scenario.

Theoretical Insight into the Biodegradation of Solitary Oil Microdroplets Moving through a Water Column.

In the aftermath of oil spills in the sea, clouds of droplets drift into the seawater column and are carried away by sea currents. The fate of the drifting droplets is determined by natural attenuation processes, mainly dissolution into the seawater and biodegradation by oil-degrading microbial communities. Specifically, microbes have developed three fundamental strategies for accessing and assimilating oily substrates. Depending on their affinity for the oily phase and ability to proliferate in multicellular structures, microbes might either attach to the oil surface and directly uptake compounds from the oily phase, or grow suspended in the aqueous phase consuming solubilized oil, or form three-dimensional biofilms over the oil–water interface. In this work, a compound particle model that accounts for all three microbial strategies is developed for the biodegradation of solitary oil microdroplets moving through a water column. Under a set of educated hypotheses, the hydrodynamics and solute transport problems are amenable to analytical solutions and a closed-form correlation is established for the overall dissolution rate as a function of the Thiele modulus, the Biot number and other key parameters. Moreover, two coupled ordinary differential equations are formulated for the evolution of the particle size and used to investigate the impact of the dissolution and biodegradation processes on the droplet shrinking rate.

Natural attenuation of petroleum hydrocarbons-a study of biodegradation effects in groundwater (Vitanovac, Serbia).

The role of natural attenuation processes in groundwater contamination by petroleum hydrocarbons is of intense scientific and practical interest. This study provides insight into the biodegradation effects in groundwater at a site contaminated by kerosene (jet fuel) in 1993 (Vitanovac, Serbia). Total petroleum hydrocarbons (TPH), hydrochemical indicators (O2, NO3-, Mn, Fe, SO42-, HCO3-), δ13C of dissolved inorganic carbon (DIC), and other parameters were measured to demonstrate biodegradation effects in groundwater at the contaminated site. Due to different biodegradation mechanisms, the zone of the lowest concentrations of electron acceptors and the zone of the highest concentrations of metabolic products of biodegradation overlap. Based on the analysis of redox-sensitive compounds in groundwater samples, redox processes ranged from strictly anoxic (methanogenesis) to oxic (oxygen reduction) within a short distance. The dependence of groundwater redox conditions on the distance from the source of contamination was observed. δ13C values of DIC ranged from - 15.83 to - 2.75‰, and the most positive values correspond to the zone under anaerobic and methanogenic conditions. Overall, results obtained provide clear evidence on the effects of natural attenuation processes-the activity of biodegradation mechanisms in field conditions.