Modeling the GCxGC Elution Patterns of a Hydrocarbon Structure Library To Innovate Environmental Risk Assessments of Petroleum Substances.

Comprehensive two-dimensional gas chromatography (GCxGC) offers unrivaled separation of petroleum substances, which can contain thousands of constituents or more. However, interpreting substance compositions from GCxGC data is costly and requires expertise. To facilitate environmental risk assessments, industries provide aggregated compositional information known as "hydrocarbon blocks" (HCBs), but these proprietary methods do not transparently associate the HCBs with GCxGC chromatogram data. These obstacles frustrate efforts to study the environmental risks of petroleum substances and associated environmental samples. To address this problem, we developed a GCxGC elution model for user-defined petroleum substance compositions. We calibrated the elution model to experimental GCxGC retention times of 56 known hydrocarbons by fitting three tunable model parameters to two candidate instrument methods. With the calibrated model, we simulated retention times for a library of 15,447-15,455 hydrocarbon structures (plus 40-48 predicted as chromatographically unretained) spanning 11 classes of petroleum substance constituents in the C10-C30 range. The resulting simulation data reveal that GCxGC retention times are quantitatively associated with hydrocarbon class and carbon number information throughout the GCxGC chromatogram. These innovations enable the development of transparent and efficient technical methods to investigate the chemical compositions and environmental properties of petroleum substances, including in environmental and lab-weathered samples.

Application of the Target Lipid Model to Assess Toxicity of Heterocyclic Aromatic Compounds to Aquatic Organisms.

Heterocyclic aromatic compounds can be found in crude oil and coal and often co-exist in environmental samples with their homocyclic aromatic counterparts. The target lipid model (TLM) is a modeling framework that relates aquatic toxicity to the octanol-water partition coefficient (KOW ) that has been calibrated and validated for hydrocarbons. A systematic analysis of the applicability of the TLM to heterocyclic aromatic compounds has not been performed. The objective of the present study was to compile reliable toxicity data for heterocycles and determine whether observed toxicity could be successfully described by the TLM. Results indicated that the TLM could be applied to this compound class by adopting an empirically derived coefficient that accounts for partitioning between water and lipid. This coefficient was larger than previously reported for aromatic hydrocarbons, indicating that these heterocyclic compounds exhibit higher affinity to target lipid and toxicity. A mechanistic evaluation confirmed that the hydrogen bonding accepting moieties of the heteroatoms helped explain differences in partitioning behavior. Given the TLM chemical class coefficient reported in the present study, heterocyclic aromatics can now be explicitly incorporated in TLM-based risk assessments of petroleum substances, other products, or environmental media containing these compounds. Environ Toxicol Chem 2021;40:3000-3009. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Improving our understanding of the environmental persistence of chemicals.

Significant progress has been made in the scientific understanding of factors that influence the outcome of biodegradation tests used to assess the persistence (P) of chemicals. This needs to be evaluated to assess whether recently acquired knowledge could enhance existing regulations and environmental risk assessments. Biodegradation tests have limitations, which are accentuated for "difficult-to-test" substances, and failure to recognize these can potentially lead to inappropriate conclusions regarding a chemical's environmental persistence. Many of these limitations have been previously recognized and discussed in a series of ECETOC reports and workshops. These were subsequently used to develop a series of research projects designed to address key issues and, where possible, propose methods to mitigate the limitations of current assessments. Here, we report on the output of a Cefic LRI-Concawe Workshop held in Helsinki on September 27, 2018. The objectives of this workshop were to disseminate key findings from recent projects and assess how new scientific knowledge can potentially support and improve assessments under existing regulatory frameworks. The workshop provided a unique opportunity to initiate a process to reexamine the fundamentals of degradation and what current assessment methods can achieve by (1) providing an overview of the key elements and messages coming from recent research initiatives and (2) stimulating discussion regarding how these interrelate and how new findings can be developed to improve persistence assessments. Opportunities to try and improve understanding of factors affecting biodegradation assessments and better understanding of the persistence of chemicals (particularly UVCBs [substances of unknown or variable composition, complex reaction products, or biological materials]) were identified, and the workshop acted as a catalyst for further multistakeholder activities and engagements to take the persistence assessment of chemicals into the 21st century. Integr Environ Assess Manag 2021;17:1123-1135. © 2021 European Petroleum Refiners Association - Concawe Division. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Acritical review and weight of evidence approach for assessing the bioaccumulation of phenanthrene in aquatic environments.

Bioaccumulation (B) assessment is challenging because there are various B-metrics from laboratory and field studies, multiple criteria and thresholds for classifying bioaccumulative (B), very bioaccumulative (vB), and not bioaccumulative (nB) chemicals, as well as inherent variability and uncertainty in the data. These challenges can be met using a weight of evidence (WoE) approach. The Bioaccumulation Assessment Tool (BAT) provides a transparent WoE assessment framework that follows Organisation for Economic Co-operation and Development (OECD) principles for performing a WoE analysis. The BAT guides an evaluator through the process of data collection, generation, evaluation, and integration of various lines of evidence (LoE) (i.e., B-metrics) to inform decision-making. Phenanthrene (PHE) is a naturally occurring chemical for which extensive B and toxicokinetics data are available. A B assessment for PHE using the BAT is described that includes a critical evaluation of 74 measured in vivo LoE for fish and invertebrate species from laboratory and field studies. The number of LoE are reasonably well balanced across taxa (i.e., fish and invertebrates) and the different B-metrics. Additionally, in silico and in vitro biotransformation rate estimates and corresponding model-predicted B-metrics are included as corroborating evidence. Application of the BAT provides a consistent, coherent, and scientifically defensible WoE evaluation to conclude that PHE is not bioaccumulative (nB) because the overwhelming majority of the bioconcentration, bioaccumulation, and biomagnification metrics for both fish and invertebrates are below regulatory thresholds. An analysis of the relevant data using fugacity ratios is also provided, showing that PHE does not biomagnify in aquatic food webs. The critical review identifies recommendations to increase the consistency of B assessments, such as improved standardization of B testing guidelines, data reporting requirements for invertebrate studies, and consideration of temperature and salinity effects on certain B-metrics. Integr Environ Assess Manag 2021;17:911-925. © 2021 Concawe. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Assessing toxicity of hydrophobic aliphatic and monoaromatic hydrocarbons at the solubility limit using novel dosing methods.

Reliable delineation of aquatic toxicity cut-offs for poorly soluble hydrocarbons is lacking. In this study, vapor and passive dosing methods were applied in limit tests with algae and daphnids to evaluate the presence or absence of chronic effects at exposures corresponding to the water solubility for representative hydrocarbons from five structural classes: branched alkanes, mono, di, and polynaphthenic (cyclic) alkanes and monoaromatic naphthenic hydrocarbons (MANHs). Algal growth rate and daphnid immobilization, growth and reproduction served as the chronic endpoints investigated. Results indicated that the dosing methods applied were effective for maintaining mean measured exposure concentrations within a factor of two or higher of the measured water solubility of the substances investigated. Chronic effects were not observed for hydrocarbons with an aqueous solubility below approximately 5 µg/L. This solubility cut-off corresponds to structures consisting of 13-14 carbons for branched and cyclic alkanes and 16-18 carbons for MANHs. These data support reliable hazard and risk evaluation of hydrocarbon classes that comprise petroleum substances and the methods described have broad applicability for establishing empirical solubility cut-offs for other classes of hydrophobic substances. Future work is needed to understand the role of biotransformation on the observed presence or absence of toxicity in chronic tests.

Regulations for chromium emissions to the aquatic environment in Europe and elsewhere.

Chromium is a controversial element, since it has been classified as essential trace element, to chemically and biologically inert compound, to potent intoxicator. Concerns have been risen for chromium effects on human and aquatic life because chromium has been accused for genotoxicity and carcinogenesis. Metals and their ions or complexes (and thus chromium substances) are included in the indicative list of main pollutants (Annex VIII of the Water Framework Directive (2000/60/EC)). Biological effects of chromium are strongly depended on chromium speciation. No universal CrIII or CrVI discharge limits to the aquatic environment have been suggested by the EU. International bodies within the EU, such as the Helsinki Commission and the Oslo-Paris Convention, have issued recommendations on chromium discharge levels. National CrVI and CrIII discharge limits vary in each EU Member State with respect to the receiving water body (marine water, lake, river, sewer system). The maximum discharge limit to the aquatic environment in EU is 1 and 5 mg L-1 for CrVI and Crtotal, respectively. The present work summarizes EU legislation, with respect to the discharge limits to the aquatic environment for CrVI and CrIII. EU national limits that are currently effective are presented and compared to the limits in other parts of the world, such as Australia, Asia, USA, Latin America and South Africa. It is wise that future perspective of chromium policy should differentiate between CrIII and CrVI discharge limits to the aquatic environment, as analytical techniques become more sensitive and chromium speciation specific, and environmental awareness rises.

Is the Arrhenius-correction of biodegradation rates, as recommended through REACH guidance, fit for environmentally relevant conditions? An example from petroleum biodegradation in environmental systems.

Biodegradation is a major determinant of chemical persistence in the environment and an important consideration for PBT and environmental risk assessments. It is influenced by several environmental factors including temperature and microbial community structure. According to REACH guidance, a temperature correction based on the Arrhenius equation is recommended for chemical persistence data not performed at the recommended EU mean surface water temperature. Such corrections, however, can lead to overly conservative P/vP assessments. In this paper, the relevance of this temperature correction is assessed for petroleum hydrocarbons, using measured surface water (marine and freshwater) degradation half-time (DT50) and degradation half-life (HL) data compiled from relevant literature. Stringent screening criteria were used to specifically select data from biodegradation tests containing indigenous microbes and conducted at temperatures close to their ambient sampling temperature. As a result, ten independent studies were identified, with 993 data points covering 326 hydrocarbon constituents. These data were derived from tests conducted with natural seawater, or freshwater, at temperatures ranging from 5 to 21 °C. Regressions were performed on the full hydrocarbon dataset and on several individual hydrocarbons. The results were compared to the trend as predicted by the Arrhenius equation and using the activation energy (Ea) as recommend in the REACH Guidance. The comparison shows that the correction recommended in REACH Guidance over predicts the effect of temperature on hydrocarbon biodegradation. These results contrast with temperature manipulated inocula where the test temperature is different from the ambient sampling temperature. In these manipulated systems, the effect of temperature follows the Arrhenius equation more closely. In addition, a more striking effect of temperature on the lag phase was observed with longer lag phases more apparent at lower temperatures. This indicates that the effect of temperature may indeed be even lower when considering hydrocarbon biodegradation without the initial lag phase.

Electrochemical treatment of industrial sulfidic spent caustic streams for sulfide removal and caustic recovery.

Alkaline spent caustic streams (SCS) produced in the petrochemical and chemical manufacturing industry, contain high concentrations of reactive sulfide (HS-) and caustic soda (NaOH). Common treatment methods entail high operational costs while not recovering the possible resources that SCS contain. Here we studied the electrochemical treatment of SCS from a chemical manufacturing industry in an electrolysis cell, aiming at anodic HS- removal and cathodic NaOH, devoid of sulfide, recovery. Using a synthetic SCS we first evaluated the HS- oxidation product distribution over time, as well as the HS- removal and the NaOH recovery, as a function of current density. In a second step, we investigated the operational aspects of such treatment for the industrial SCS, under 300 A m-2 fixed current density. In an electrolysis cell receiving 205 ±â€¯60 g S L-1 d-1 HS- over 20 days of continuous operation, HS- was removed with a 38.0 ±â€¯7.7 % removal and ∼80 % coulombic efficiency, with a concomitant recovery of a ∼12 wt.% NaOH solution. The low cell voltage obtained (1.75 ±â€¯0.12 V), resulted in low energy requirements of 3.7 ±â€¯0.6 kW h kg-1 S and 6.3 ±â€¯0.4 kW h kg-1 NaOH and suggests techno-economic viability of this process.

Electrochemical tap water softening: A zero chemical input approach.

Electrochemical water softening was proposed as a sustainable alternative for ion exchange softening, avoiding the input of salt to drinking water and the production of a concentrated brine. Here we demonstrated two novel modes of operation combining an electrochemical cell with a fluidized bed crystallizer. The first approach relied on an electrochemical cell consisting of an anode and cathode separated by a cation or anion exchange membrane. The feed water was first directed into a crystallizer where it was blended with alkaline cathode effluent. The effluent of the crystallizer, softened water, was in part recirculated to the cathode to generate alkalinity, in part to the anode compartment, where the pH was again decreased. Average removal efficiencies for calcium and magnesium of 75-86% and 7-21% respectively, could be sustainably reached, at a specific energy consumption of 7.0-10.1 kWh kg-1 CaCO3 (0.86-1.39 kWh m-3 water). This configuration allowed reagent-free water softening, albeit with an effluent with a pH between 3.0 and 3.6. In a second mode of operation, the process influent to soften was also directed to the crystallizer and recirculated over the cathode, which was separated from the anode using an anion exchange membrane. In this mode of operation, the cathode effluent was sent through the crystallizing unit, and the anode compartment was operated in closed-loop. Average calcium and magnesium removal efficiencies of 73-78% and 40-44% were obtained at specific energy consumptions of 5.8-7.5 kWh kg-1 CaCO3 (0.77-0.88 kWh m-3 water). Although the softened water had an elevated pH (∼9.4), the advantage of this configuration is concomitant removal of anions and the formation of acids/disinfectant in the anode compartment. Both methods of operation thus showed reagent-free water softening at a relatively low specific energy consumption. These novel methods of softening could be used in remote locations where access to chemicals or discharge of ion exchange brines proves to be difficult, or in case addition of chemicals for softening is unwanted. Further research is needed to further decrease the specific energy consumption during long-term operation.

UVCB substances II: Development of an endpoint-nonspecific procedure for selection of computationally generated representative constituents.

Substances of unknown or variable composition, complex reaction products, and biological materials (UVCBs) comprise approximately 40% of all registered substances submitted to the European Chemicals Agency. One of the main characteristics of UVCBs is that they have no unique representation. Industry scientists who are part of the scientific community have been working with academics and consultants to address the problem of a lack of a defined structural description. It has been acknowledged that one of the obstacles is the large number of possible structural isomers. We have recently proposed and published a methodology, based on the generic substance identifiers, to address this issue. The methodology allows for the coding of constituents, their generation, calculation of important characteristics of UVCB constituents, and selection of representative constituents. In the present study we introduce a statistical selection of the minimum number of generated constituents representing a UVCB. This representative sample was selected in such a way that the structural variability and the properties of concern of the UVCB were approximated within a predefined tolerable error. The aim of the statistical selection was to enable the assessment of UVCB substances by decreasing the number of constituents that need to be evaluated. The procedure, which was shown to be endpoint-independent, was validated theoretically and on real case studies. Environ Toxicol Chem 2019;38:682-694. © 2019 SETAC.

Anode potential selection for sulfide removal in contaminated marine sediments.

Sulfate reducing microorganisms are typically involved in hydrocarbon biodegradation in the sea sediment, with their metabolism resulting in the by-production of toxic sulfide. In this context, it is of utmost importance identifying the optimal value for anodic potential which ensures efficient toxic sulfide removal. Along this line, in this study the (bio)electrochemical removal of sulfide was tested at anodic potentials of -205 mV, +195 mV and +300 mV (vs Ag/AgCl), also in the presence of a pure culture of the sulfur-oxidizing bacterium Desulfobulbus propionicus. Current production, sulfide concentration and sulfate concentration were monitored over time. At the end of the experiment sulfur deposition on the electrodes and the microbial communities were characterized by SEM-EDS and by next generation sequencing of the 16S rRNA gene respectively. Results confirmed that current production was linked to sulfide removal and D. propionicus promoted back oxidation of deposited sulfur to sulfate. The highest electron recovery was observed at +195 mV vs Ag/AgCl, and the lowest sulfur deposition was obtained at -205 mV vs Ag/AgCl anode polarization.

Bridging spatially segregated redox zones with a microbial electrochemical snorkel triggers biogeochemical cycles in oil-contaminated River Tyne (UK) sediments.

Marine sediments represent an important sink for a number of anthropogenic organic contaminants, including petroleum hydrocarbons following an accidental oil spill. Degradation of these compounds largely depends on the activity of sedimentary microbial communities linked to biogeochemical cycles, in which abundant elements such as iron and sulfur are shuttled between their oxidized and reduced forms. Here we show that introduction of a small electrically conductive graphite rod ("the electrochemical snorkel") into an oil-contaminated River Tyne (UK) sediment, so as to create an electrochemical connection between the anoxic contaminated sediment and the oxygenated overlying water, has a large impact on the rate of metabolic reactions taking place in the bulk sediment. The electrochemical snorkel accelerated sulfate reduction processes driven by organic contaminant oxidation and suppressed competitive methane-producing reactions. The application of a comprehensive suite of chemical, spectroscopic, biomolecular and thermodynamic analyses suggested that the snorkel served as a scavenger of toxic sulfide via a redox interaction with the iron cycle. Taken as a whole, the results of this work highlight a new strategy for controlling biological processes, such as bioremediation, through the manipulation of the electron flows in contaminated sediments.

Electrochemical oxidation of iron and alkalinity generation for efficient sulfide control in sewers.

The addition of iron salts is one of the most commonly used dosing strategies for sulfide control in sewers. However, iron salts decrease the sewage pH which not only reduces the effectiveness of sulfide precipitation but also enhances the release of residual sulfide to the sewer atmosphere. Equally important, concentrated iron salt solutions are corrosive and their frequent transport, handling, and on-site storage often come with Occupational Health and Safety (OH&S) concerns. Here, we experimentally demonstrated a novel sulfide control approach using electrochemical systems with parallel placed iron electrodes. This enabled combining anodic dissolved iron species release with cathodic hydroxyl anion production, which alleviates all the aforementioned concerns. A long-term experiment was successfully carried out achieving an average sulfide removal efficiency of 95.4 ± 4.4% at low voltage input of 2.90 ± 0.54 V over the course of 8 weeks. This electrochemical method was demonstrated to successfully achieve efficient sulfide control. In addition, it increases the sewage pH, thereby overcoming the drawbacks associated with the pH decrease in the case of conventional iron salt dosing. Ferrous ions were produced at an overall coulombic efficiency (CE) of 98.2 ± 1.2%, whereas oxygen evolution and direct sulfide oxidation were not observed. Short-term experiments showed that increasing either inter-electrode gap or current density increased the cell voltage associated with the increase in the ohmic drop of the system. Overall, this study highlights the practical potential of in-situ generation of dissolved iron species and simultaneous hydroxyl anion generation for efficient sulfide control in sewers.

Electrobioremediation of oil spills.

Annually, thousands of oil spills occur across the globe. As a result, petroleum substances and petrochemical compounds are widespread contaminants causing concern due to their toxicity and recalcitrance. Many remediation strategies have been developed using both physicochemical and biological approaches. Biological strategies are most benign, aiming to enhance microbial metabolic activities by supplying limiting inorganic nutrients, electron acceptors or donors, thus stimulating oxidation or reduction of contaminants. A key issue is controlling the supply of electron donors/acceptors. Bioelectrochemical systems (BES) have emerged, in which an electrical current serves as either electron donor or acceptor for oil spill bioremediation. BES are highly controllable and can possibly also serve as biosensors for real time monitoring of the degradation process. Despite being promising, multiple aspects need to be considered to make BES suitable for field applications including system design, electrode materials, operational parameters, mode of action and radius of influence. The microbiological processes, involved in bioelectrochemical contaminant degradation, are currently not fully understood, particularly in relation to electron transfer mechanisms. Especially in sulfate rich environments, the sulfur cycle appears pivotal during hydrocarbon oxidation. This review provides a comprehensive analysis of the research on bioelectrochemical remediation of oil spills and of the key parameters involved in the process.

Electrochemical sulfide removal and caustic recovery from spent caustic streams.

Spent caustic streams (SCS) are produced during alkaline scrubbing of sulfide containing sour gases. Conventional methods mainly involve considerable chemical dosing or energy expenditures entailing high cost but limited benefits. Here we propose an electrochemical treatment approach involving anodic sulfide oxidation preferentially to sulfur coupled to cathodic caustic recovery using a two-compartment electrochemical system. Batch experiments showed sulfide removal efficiencies of 84 ± 4% with concomitant 57 ± 4% efficient caustic production in the catholyte at a final concentration of 6.4 ± 0.1 wt% NaOH (1.6 M) at an applied current density of 100 A m(-2). Subsequent long-term continuous experiments showed that stable cell voltages (i.e. 2.7 ± 0.1 V) as well as constant sulfide removal efficiencies of 67 ± 5% at a loading rate of 47 g(S) L(-1) h(-1) were achieved over a period of 77 days. Caustic was produced at industrially relevant strengths for scrubbing (i.e. 5.1 ± 0.9 wt% NaOH) at current efficiencies of 96 ± 2%. Current density between 0 and 200 A m(-2) and sulfide loading rates of 50-200 g(S) L(-1) d(-1) were tested. The higher the current density the more oxidized the sulfur species produced and the higher the sulfide oxidation. On the contrary, high loading rate resulted in a reduction of sulfide oxidation efficiency. The results obtained in this study together with engineering calculations show that the proposed process could represent a cost-effective approach for sodium and sulfur recovery from SCS.

Anodes Stimulate Anaerobic Toluene Degradation via Sulfur Cycling in Marine Sediments.

Hydrocarbons released during oil spills are persistent in marine sediments due to the absence of suitable electron acceptors below the oxic zone. Here, we investigated an alternative bioremediation strategy to remove toluene, a model monoaromatic hydrocarbon, using a bioanode. Bioelectrochemical reactors were inoculated with sediment collected from a hydrocarbon-contaminated marine site, and anodes were polarized at 0 mV and +300 mV (versus an Ag/AgCl [3 M KCl] reference electrode). The degradation of toluene was directly linked to current generation of up to 301 mA m(-2) and 431 mA m(-2) for the bioanodes polarized at 0 mV and +300 mV, respectively. Peak currents decreased over time even after periodic spiking with toluene. The monitoring of sulfate concentrations during bioelectrochemical experiments suggested that sulfur metabolism was involved in toluene degradation at bioanodes. 16S rRNA gene-based Illumina sequencing of the bulk anolyte and anode samples revealed enrichment with electrocatalytically active microorganisms, toluene degraders, and sulfate-reducing microorganisms. Quantitative PCR targeting the α-subunit of the dissimilatory sulfite reductase (encoded by dsrA) and the α-subunit of the benzylsuccinate synthase (encoded by bssA) confirmed these findings. In particular, members of the family Desulfobulbaceae were enriched concomitantly with current production and toluene degradation. Based on these observations, we propose two mechanisms for bioelectrochemical toluene degradation: (i) direct electron transfer to the anode and/or (ii) sulfide-mediated electron transfer.

Electrical stimulation improves microbial salinity resistance and organofluorine removal in bioelectrochemical systems.

Fed batch bioelectrochemical systems (BESs) based on electrical stimulation were used to treat p-fluoronitrobenzene (p-FNB) wastewater at high salinities. At a NaCl concentration of 40 g/liter, p-FNB was removed 100% in 96 h in the BES, whereas in the biotic control (BC) (absence of current), p-FNB removal was only 10%. By increasing NaCl concentrations from 0 g/liter to 40 g/liter, defluorination efficiency decreased around 40% in the BES, and in the BC it was completely ceased. p-FNB was mineralized by 30% in the BES and hardly in the BC. Microorganisms were able to store 3.8 and 0.7 times more K(+) and Na(+) intracellularly in the BES than in the BC. Following the same trend, the ratio of protein to soluble polysaccharide increased from 3.1 to 7.8 as the NaCl increased from 0 to 40 g/liter. Both trends raise speculation that an electrical stimulation drives microbial preference toward K(+) and protein accumulation to tolerate salinity. These findings are in accordance with an enrichment of halophilic organisms in the BES. Halobacterium dominated in the BES by 56.8% at a NaCl concentration of 40 g/liter, while its abundance was found as low as 17.5% in the BC. These findings propose a new method of electrical stimulation to improve microbial salinity resistance.

Removal and toxicity reduction of naphthenic acids by ozonation and combined ozonation-aerobic biodegradation.

A commercial naphthenic acids (NAs) mixture (TCI Chemicals) and five model NA compounds were ozonated in a semibatch mode. Ozonation of 25 and 35 mg/L NA mixture followed pseudo first-order kinetics (k(obs)=0.11±0.008 min(-1); r(2)=0.989) with a residual NAs concentration of about 5 mg/L. Ozone reacted preferentially with NAs of higher cyclicity and molecular weight and decreased both cyclicity and the acute Microtox® toxicity by 3.3-fold. The ozone reactivity with acyclic and monocyclic model NAs varied and depended on other structural features, such as branching and the presence of tertiary or quaternary carbons. Batch aerobic degradation of unozonated NA mixture using a NA-enriched culture resulted in 83% NA removal and a 6.7-fold decrease in toxicity, whereas a combination of ozonation-biodegradation resulted in 89% NA removal and a 15-fold decrease in toxicity. Thus, ozonation of NA-bearing waste streams coupled with biodegradation are effective treatment processes.

Effects of chromium on activated sludge and on the performance of wastewater treatment plants: A review.

Chromium is a heavy metal of commercial importance, thus significant amounts are released in wastewaters. Chromium in wastewaters and in the aquatic environment is primarily encountered in oxidation stages +3 (Cr((III))) and +6 (Cr((VI))). Recent publications suggest that Cr((VI)) compounds are more toxic than Cr((III)) ones, while Cr((III)) has been identified as trace element, at least for complex organisms. With respect to chromium species mobility, Cr((VI)) can cross cellular membranes, which then may be oxidized to Cr((III)) and react with intracellular biomolecules. Clear conclusions cannot be derived about the critical chromium concentrations that affect activated sludge growth, as the latter is a function of a number of factors. Broadly, may be supported that activated sludge growth is stimulated at Cr((III)) concentrations up to 15 mg L(-1), above which is inhibited, with lethal doses lying above 160 mg Cr((III)) L(-1). On the other hand, literature data on Cr((VI)) effects on activated sludge are even more controversial. A number of reports support that Cr((VI)) is toxic to activated sludge at concentrations above 5 mg L(-1), while others report growth stimulation at concentrations up to 25 mg L(-1). However, all reports agree that Cr((VI)) is definitely an activated sludge growth inhibitor at higher concentrations, while 80 mg Cr((VI)) L(-1) have been identified as lethal dose. A number of factors have been identified to influence chromium toxicity on activated sludge, such as, pH, biomass concentration, presence of organic substances or other heavy metals, acclimation process, exposure time, etc. Naturally, the presence of chromium species in wastewaters may affect the performance of wastewater treatment plants often causing malfunctions, particularly for industrial wastewaters containing relatively high chromium concentrations. The present work reviews in a critical way the published literature on chromium effects on activated sludge, and on the operation of wastewater treatment plants.

Sulfide removal in wastewater from petrochemical industries by autotrophic denitrification.

An alternative flowchart for the biological removal of hydrogen sulfide from oil-refining wastewater is presented; autotrophic denitrification in a multi-stage treatment plant was utilized. A pilot-scale plant was fed with a mixture of the following constituents: (a) original wastewater from an oil refining industry (b), the effluent of the existing nitrification-stage treatment plant and (c) sulfide in the form of Na2S. Anoxic sulfide to sulfate oxidation, with nitrate as a terminal electron acceptor, proved very successful, as incoming concentrations of 110 mg S2-/L were totally converted to SO(4)2-. At complete denitrification, the concentration of S2- in the reactor effluent was less than 0.1mg/L. Fluctuating S2- concentration in the feed could be tolerated without any problems, as the accumulated sulfide in the effluent of the denitrification stage is oxidized aerobically in a subsequent activated-sludge treatment stage. This alternative new treatment scheme was further introduced at the refinery's wastewater processing plant. Thus, complete H2S removal is now accomplished by the combination of the proposed biological method and the existing stripping with CO2. As a result, stripping, and thus its cost, is reduced by 70%.