Analysis of Legacy and Novel Neutral Per- and Polyfluoroalkyl Substances in Soils from an Industrial Manufacturing Facility.

Per- and polyfluoroalkyl substances (PFASs) have been detected in an array of environmental media due to their ubiquitous use in industrial and consumer products as well as potential release from fluorochemical manufacturing facilities. During their manufacture, many fluorotelomer (FT) facilities rely on neutral intermediates in polymer production including the FT-alcohols (FTOHs). These PFAS are known to transform to the terminal acids (perfluoro carboxylic acids; PFCAs) at rates that vary with environmental conditions. In the current study on soils from a FT facility, we employed gas chromatography coupled with conventional- and high-resolution mass spectrometry (GC-MS and GC-HRMS) to investigate the profile of these precursor compounds, the intermediary secondary alcohols (sFTOHs), FT-acrylates (FTAcr), and FT-acetates (FTAce) in soils around the former FT-production facility. Of these precursors, the general trend in detection intensity was [FTOHs] > [sFTOHs] > [FTAcrs], while for the FTOHs, homologue intensities generally were [12:2 FTOH] > [14:2 FTOH] > [16:2 FTOH] > [10:2 FTOH] > [18:2 FTOH] > [20:2 FTOH] > [8:2 FTOH] ∼ [6:2 FTOH]. The corresponding terminal acids were also detected in all soil samples and positively correlated with the precursor concentrations. GC-HRMS confirmed the presence of industrial manufacturing byproducts such as FT-ethers and FT-esters and aided in the tentative identification of previously unreported dimers and other compounds. The application of GC-HRMS to the measurement and identification of precursor PFAS is in its infancy, but the methodologies described here will help refine its use in tentatively identifying these compounds in the environment.

Environmental Fate of Cl-PFPECAs: Predicting the Formation of PFAS Transformation Products in New Jersey Soils.

Although next-generation per- and polyfluorinated substances (PFAS) were designed and implemented as safer and environmentally degradable alternatives to "forever" legacy PFAS, there is little evidence to support the actual transformation of these compounds and less evidence of the safety of transformed products in the environment. Multiple congeners of one such PFAS alternative, the chloro-perfluoropolyether carboxylates (Cl-PFPECAs), have been found in New Jersey soils surrounding a manufacturing facility. These compounds are ideal candidates for investigating environmental transformation due to the existence of potential reaction centers including a chlorinated carbon and ether linkages. Transformation products of the chemical structures of this class of compounds were predicted based on analogous PFAS transformation pathways documented in peer-reviewed literature. Potential reaction products were used as the basis for high-resolution mass-spectrometric suspect screening of the soils. Suspected transformation products of multiple congeners, the Cl-PFPECAs, including H-PFPECAs, epox-PFPECAs, and diOH-PFPECAs, were tentatively observed in these screenings. Although ether linkages have been hypothesized as potential reaction centers under environmental conditions, to date, no documentation of ether scission has been identified. Despite exhaustive scrutiny of the high-resolution data for our Cl-PFPECA-laden soils, we found no evidence of ether scission.

Development of a PFAS reaction library: identifying plausible transformation pathways in environmental and biological systems.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are used in many consumer applications due to their stain repellency, surfactant properties, ability to form water-proof coatings and use in fire suppression. The production, application, transport, use and disposal of PFAS and PFAS-treated products have resulted in their wide-spread occurrence in environmental and biological systems. Concern over exposure to PFAS and their transformation products and metabolites has necessitated the development of tools to predict the transformation of PFAS in environmental systems and metabolism in biological systems. We have developed reaction libraries for predicting transformation products and metabolites in a variety of environmental and biological reaction systems. These reaction libraries are based on generalized reaction schemes that encode the process science of PFAS reported in the peer-reviewed literature. The PFAS reaction libraries will be executed through the Chemical Transformation Simulator, a web-based tool that is available to the public. These reaction libraries are intended for predicting the environmental transformation and metabolism of PFAS only.

Per- and polyfluoroalkyl substances in the environment.

Over the past several years, the term PFAS (per- and polyfluoroalkyl substances) has grown to be emblematic of environmental contamination, garnering public, scientific, and regulatory concern. PFAS are synthesized by two processes, direct fluorination (e.g., electrochemical fluorination) and oligomerization (e.g., fluorotelomerization). More than a megatonne of PFAS is produced yearly, and thousands of PFAS wind up in end-use products. Atmospheric and aqueous fugitive releases during manufacturing, use, and disposal have resulted in the global distribution of these compounds. Volatile PFAS facilitate long-range transport, commonly followed by complex transformation schemes to recalcitrant terminal PFAS, which do not degrade under environmental conditions and thus migrate through the environment and accumulate in biota through multiple pathways. Efforts to remediate PFAS-contaminated matrices still are in their infancy, with much current research targeting drinking water.

Prioritizing Direct Photolysis Products Predicted by the Chemical Transformation Simulator: Relative Reasoning and Absolute Ranking.

The United States Environmental Protection Agency's Chemical Transformation Simulator (CTS) platform implemented the first freely available reaction library to predict direct photolysis products of organic contaminants in aquatic systems. However, the initial version of the reaction library did not differentiate the formation likelihood of each predicted product, and therefore, the number of predicted products that are not observed tended to exponentially increase with the prediction generation. To alleviate this problem, we first employed relative reasoning algorithms to remove unlikely products. We then ranked different reaction schemes according to their transformation kinetics and removed slowly forming products. Applying the two strategies improved the precision (the percentage of correctly predicted products over all predicted products) by 34% and 53% for the internal evaluation set and the external evaluation set, respectively, when products from three generations were considered. This improved library also revealed new research directions to improve predictions of the dominant phototransformation products.

Quantitative structure activity relationships (QSARs) and machine learning models for abiotic reduction of organic compounds by an aqueous Fe(II) complex.

Due to the increasing diversity of organic contaminants discharged into anoxic water environments, reactivity prediction is necessary for chemical persistence evaluation for water treatment and risk assessment purposes. Almost all quantitative structure activity relationships (QSARs) that describe rates of contaminant transformation apply only to narrowly-defined, relatively homogenous families of reactants (e.g., dechlorination of alkyl halides). In this work, we develop predictive models for abiotic reduction of 60 organic compounds with diverse reducible functional groups, including nitroaromatic compounds (NACs), aliphatic nitro-compounds (ANCs), aromatic N-oxides (ANOs), isoxazoles (ISXs), polyhalogenated alkanes (PHAs), sulfoxides and sulfones (SOs), and others. Rate constants for their reduction were measured using a model reductant system, Fe(II)-tiron. Qualitatively, the rates followed the order NACs > ANOs ≈ ISXs ≈ PHAs > ANCs > SOs. To develop QSARs, both conventional chemical descriptor-based and machine learning (ML)-based approaches were investigated. Conventional univariate QSARs based on a molecular descriptor ELUMO (energy of the lowest-unoccupied molecular orbital) gave good correlations within classes. Multivariate QSARs combining ELUMO with Abraham descriptors for physico-chemical properties gave slightly improved correlations within classes for NCs and NACs, but little improvement in correlation within other classes or among classes. The ML model obtained covers reduction rates for all classes of compounds and all of the conditions studied with the prediction accuracy similar to those of the conventional QSARs for individual classes (r2 = 0.41-0.98 for univariate QSARs, 0.71-0.94 for multivariate QSARs, and 0.83 for the ML model). Both approaches required a scheme for a priori classification of the compounds for model training. This work offers two alternative modeling approaches to comprehensive abiotic reactivity prediction for persistence evaluation of organic compounds in anoxic water environments.

Reaction Library to Predict Direct Photochemical Transformation Products of Environmental Organic Contaminants in Sunlit Aquatic Systems.

Cheminformatics-based applications to predict transformation pathways of environmental contaminants are useful to quickly prioritize contaminants with potentially toxic/persistent products. Direct photolysis can be an important degradation pathway for sunlight-absorbing compounds in aquatic systems. In this study, we developed the first freely available direct phototransformation pathway predictive tool, which uses a rule-based reaction library. Journal publications studying diverse contaminants (such as pesticides, pharmaceuticals, and energetic compounds) were systematically compiled to encode 155 reaction schemes into the reaction library. The execution result of this predictive tool was internally evaluated against 390 compounds from the compiled journal publications and externally evaluated against 138 compounds from the regulatory reports. The recall (sensitivity) and precision (selectivity) were 0.62 and 0.35, respectively, for internal evaluation, and 0.56 and 0.20, respectively, for external evaluation, when only the products formed from the first reaction step were counted. This predictive tool could help to narrow the data gaps in chemical registration/evaluation and inform future experimental studies.

Demonstration of a consensus approach for the calculation of physicochemical properties required for environmental fate assessments.

Eight software applications are compared for their performance in estimating the octanol-water partition coefficient (Kow), melting point, vapor pressure and water solubility for a dataset of polychlorinated biphenyls, polybrominated diphenyl ethers, polychlorinated dibenzodioxins, and polycyclic aromatic hydrocarbons. The predicted property values are compared against a curated dataset of measured property values compiled from the scientific literature with careful consideration given to the analytical methods used for property measurements of these hydrophobic chemicals. The variability in the predicted values from different calculators generally increases for higher values of Kow and melting point and for lower values of water solubility and vapor pressure. For each property, no individual calculator outperforms the others for all four of the chemical classes included in the analysis. Because calculator performance varies based on chemical class and property value, the geometric mean and the median of the calculated values from multiple calculators that use different estimation algorithms are recommended as more reliable estimates of the property value than the value from any single calculator.

Prediction of Hydrolysis Products of Organic Chemicals under Environmental pH Conditions.

Cheminformatics-based software tools can predict the molecular structure of transformation products using a library of transformation reaction schemes. This paper presents the development of such a library for abiotic hydrolysis of organic chemicals under environmentally relevant conditions. The hydrolysis reaction schemes in the library encode the process science gathered from peer-reviewed literature and regulatory reports. Each scheme has been ranked on a scale of one to six based on the median half-life in a data set compiled from literature-reported hydrolysis rates. These ranks are used to predict the most likely transformation route when more than one structural fragment susceptible to hydrolysis is present in a molecule of interest. Separate rank assignments are established for pH 5, 7, and 9 to represent standard conditions in hydrolysis studies required for registration of pesticides in Organisation for Economic Co-operation and Development (OECD) member countries. The library is applied to predict the likely hydrolytic transformation products for two lists of chemicals, one representative of chemicals used in commerce and the other specific to pesticides, to evaluate which hydrolysis reaction pathways are most likely to be relevant for organic chemicals found in the natural environment.

In silico environmental chemical science: properties and processes from statistical and computational modelling.

Quantitative structure-activity relationships (QSARs) have long been used in the environmental sciences. More recently, molecular modeling and chemoinformatic methods have become widespread. These methods have the potential to expand and accelerate advances in environmental chemistry because they complement observational and experimental data with "in silico" results and analysis. The opportunities and challenges that arise at the intersection between statistical and theoretical in silico methods are most apparent in the context of properties that determine the environmental fate and effects of chemical contaminants (degradation rate constants, partition coefficients, toxicities, etc.). The main example of this is the calibration of QSARs using descriptor variable data calculated from molecular modeling, which can make QSARs more useful for predicting property data that are unavailable, but also can make them more powerful tools for diagnosis of fate determining pathways and mechanisms. Emerging opportunities for "in silico environmental chemical science" are to move beyond the calculation of specific chemical properties using statistical models and toward more fully in silico models, prediction of transformation pathways and products, incorporation of environmental factors into model predictions, integration of databases and predictive models into more comprehensive and efficient tools for exposure assessment, and extending the applicability of all the above from chemicals to biologicals and materials.

Identification of Unsaturated and 2H Polyfluorocarboxylate Homologous Series and Their Detection in Environmental Samples and as Polymer Degradation Products.

A pair of homologous series of polyfluorinated degradation products have been identified, both having structures similar to perfluorocarboxylic acids but (i) having a H substitution for F on the α carbon for 2H polyfluorocarboxylic acids (2HPFCAs) and (ii) bearing a double bond between the α-ß carbons for the unsaturated PFCAs (2uPFCAs). Obtaining an authentic sample containing 2uPFOA and 2HPFOA, we optimized a mass-spectrometric multiple-reaction-monitoring (MS/MS) technique and then identified uPFCA and HPFCA homologous series in sludge-applied agricultural soils and fodder grasses for cattle grazing. Analysis of samples from a degradation experiment of commercial fluorotelomer-based polymers (FTPs), the dominant product of the fluorotelomer industry, confirmed that commercial FTPs are a potential source of uPFCAs and HPFCAs to the environment. We further confirmed the identity of the uPFCAs by imposing high-energy ionization to decarboxylate the uPFCAs then focused on the fluorinated chains in the first MS quadrupole. We also employed this high-energy ionization to decarboxylate and analyze PFCAs by MS/MS (for the first time, to our knowledge). In exploratory efforts, we report the possible detection of unsaturated perfluorooctanesulfonate in environmental samples, having a conceptual double-bond structure analogous to uPFOA. Using microcosms spiked with fluorotelomer compounds, we found 2uPFOA and 2HPFOA to be generated from unsaturated 8:2 fluorotelomer acid (8:2 FTUCA) and propose ß- and α-oxidation mechanisms for generation of these compounds from 8:2 FTUCA. In light of these experimental results, we also reexamined the proposed biodegradation pathways of 8:2 fluorotelomer alcohol.

Identifying indicators of reactivity for chemical reductants in sediments.

To conduct site-specific exposure assessments for contaminants containing reducible functional groups, it is imperative to know the identity and reactivity of chemical reductants in natural sediments and to associate their reactivity with easily measurable sediment properties. For this purpose the reactivity, as defined by pseudofirst order reduction rate constants for p-cyanonitrobenzene (pCNB), was measured in twenty-one natural sediments of different origins that were incubated to attain both anoxic (less reducing) and anaerobic (microbially reducing) conditions. The reactivity of the anoxic sediments increased with pH and an increasing amount of Fe(II) added. A good electron balance between pCNB reduction and Fe(II) consumption was observed for anaerobic sediments of high solids loading (50 g/L), but not when solids loading was 5 g/L. Based on cluster and regression analysis, pCNB reactivity in the anaerobic sediments correlates strongly with aqueous Fe(II) concentrations for sediments with low organic carbon (OC) content (<4.2%), but with dissolved OC concentrations (DOC) for the sediments with high OC content (>6.4%). These observations indicate surface-associated Fe(II) and reduced DOC are the predominant reductants in the anaerobic sediments, and that aqueous Fe(II) and DOC will serve as readily measurable indicators of pCNB reactivity in these systems.

Toward identifying the next generation of superfund and hazardous waste site contaminants.

BACKGROUND: This commentary evolved from a workshop sponsored by the National Institute of Environmental Health Sciences titled "Superfund Contaminants: The Next Generation" held in Tucson, Arizona, in August 2009. All the authors were workshop participants. OBJECTIVES: Our aim was to initiate a dynamic, adaptable process for identifying contaminants of emerging concern (CECs) that are likely to be found in future hazardous waste sites, and to identify the gaps in primary research that cause uncertainty in determining future hazardous waste site contaminants. DISCUSSION: Superfund-relevant CECs can be characterized by specific attributes: They are persistent, bioaccumulative, toxic, occur in large quantities, and have localized accumulation with a likelihood of exposure. Although still under development and incompletely applied, methods to quantify these attributes can assist in winnowing down the list of candidates from the universe of potential CECs. Unfortunately, significant research gaps exist in detection and quantification, environmental fate and transport, health and risk assessment, and site exploration and remediation for CECs. Addressing these gaps is prerequisite to a preventive approach to generating and managing hazardous waste sites. CONCLUSIONS: A need exists for a carefully considered and orchestrated expansion of programmatic and research efforts to identify, evaluate, and manage CECs of hazardous waste site relevance, including developing an evolving list of priority CECs, intensifying the identification and monitoring of likely sites of present or future accumulation of CECs, and implementing efforts that focus on a holistic approach to prevention.

Elucidating the role of electron shuttles in reductive transformations in anaerobic sediments.

Model studies have demonstrated that electron shuttles (ES) such as dissolved organic matter (DOM) can participate in the reduction of organic contaminants; however, much uncertainty exists concerning the significance of this solution phase pathway for contaminant reduction in natural systems. To compare the identity and reactivity of ES in anaerobic sediments with those in model systems, two chemical probes (4-cyano-4'-aminoazobenzene (CNAAzB) either free or covalently bound to glass beads) were synthesized that allowed for differentiation between surface-associated and solution-phase electron-transfer processes. The feasibility of these chemical probes were demonstrated in abiotic model systems (Fe(II)/Fe(III) oxide) and biotic model systems (Fe(II)/Fe(III) oxide or river sediment amended with S. putrefaciens strain cells). Experiments in the abiotic systems revealed that the addition of model hydroquinones and chemically reduced DOM increased reduction rates of free CNAAzB, whereas no enhancement in reactivity was observed with the addition of model quinones or DOM. Bound CNAAzB was also reduced by model hydroquinones and reduced DOM--but not by model quinones and untreated DOM--in the abiotic model systems, indicating that Fe(II)/Fe(III) oxides do not function as a bulk reductant forthe reduction of ES. Addition of model quinones or untreated DOM to the biotic models systems with sediment increased reduction rates of bound CNAAzB, which correlated well with the dissolved organic carbon content. In natural sediment slurries, reduction rates of bound CNAAzB correlated well with parameters for organic carbon (OC) content of both sediments and supernatants. Our results support a scenario in which reducible organic contaminants will compete with iron oxides for the electron flow generated by the microbially mediated oxidation of organic carbon and subsequent reduction of quinone functional groups associated with DOM.

Effect of natural organic matter on the reduction of nitroaromatics by Fe(II) species.

Uncertainty still exists regarding the role(s) of natural organic matter in the reduction of chemicals in anoxic environments. This work studied the effect of Suwannee river humic acid (SRHA) on the reduction of nitrobenzenes in goethite suspensions by Fe(II) species. The pseudo-first-order rate constant for the reduction of p-cyanonitrobenzene (k(CNNB)) was different for the first 3 half-lives in systems where Fe(II)aq and dissolved SRHA were equilibrated in reverse orders with goethite in suspensions. k(CNNB) and the reduction capacity of the system having SRHA added after Fe(II)aq was equilibrated with goethite was lower than that of the system for which the components were added in the reverse order. SRHA decreased the reduction capacity of the former system by oxidizing and/or complexing the surface-associated Fe(II), Fe(II)(surf), and/or hindering the access of CNNB to Fe(II)(surf). The log k(CNNB) increased linearlywith increasing concentrations of Fe(II)aq, which decreased as a result of increasing concentrations of SRHA in the system. Different k(CNNB)'s were observed for systems in which Fe(II)aq was equilibrated with goethite/SRHA suspensions for 24 and 48 h, suggesting sorbed SRHA oxidized and/or complexed Fe(II)aq. Findings suggest the concentration of Fe(II)aq and accessible Fe(ll)(surf) will influence the reduction rates of nitroaromatics in anoxic environments.

Influence of dissolved organic matter and Fe(II) on the abiotic reduction of pentachloronitrobenzene.

Nitroaromatic pesticides (NAPs) are hydrophobic contaminants that can accumulate in sediments by the deposition of suspended solids from surface waters. Fe(II) and dissolved organic matter (DOM), present in suboxic and anoxic zones of freshwater sediments, can transform NAPs in natural systems. We studied the reduction of pentachloronitrobenzene (PCNB) to pentachloroaniline (PCA) in controlled studies using Fe(II) and surface water DOM isolates from Pony Lake, Antarctica, and Suwannee River, GA, in unfiltered and 0.45 microm filtered solutions. We observed rapid reduction of PCNB to PCA in the presence of Fe(II) and DOM (t(1/2) approximately = 30 min to 4 h) and very limited reduction in DOM-only systems. DOM in unfiltered systems inhibited iron colloid formation and potentially limited the formation of reactive Fe(ll)-iron colloid surface complexes, causing reductive transformation in Fe(II)-DOM media to be slower in some cases relative to Fe(ll)-only controls. Conversely, in 0.45 microm filtered solutions, PCNB reduction in Fe(III)-DOM media was faster than the Fe(II)-only controls, suggesting that DOM enhances the reductive capacity of Fe(ll) in the absence of iron colloids. This work shows that DOM may significantly affect the reactivity of Fe(ll) toward NAPs under suboxic and anoxic conditions in natural wetland sediments.

Quantification of fluorotelomer-based chemicals in mammalian matrices by monitoring perfluoroalkyl chain fragments with GC/MS.

Perfluorocarboxylic acids (PFCAs), namely perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA), have been identified as persistent, bioaccumulative and potentially toxic compounds. The structural analog, 8-2 fluorotelomer alcohol (8-2 fTOH) is considered the probable precursor of these stable metabolites. Because simultaneous quantification is needed for volatile and non-volatile perfluorinated chemicals (PFCs) in complex matrices, a GC/MS method was developed and tested based on selected ion monitoring of perfluorinated alkyl parent chain fragment ions. Although the method requires a derivatization step, combined GC/MS analysis of PFCA-me's and FTOHs increases analytical efficiency and decreases sample analysis time. The method instrument detection limits are between 7.1 and 24.5 ng/mL extract (MTBE), and the method quantification limits are below 50 ng/mL serum or ng/g liver for all PFCs investigated. Recoveries from mouse serum and liver homogenates, which were spiked with FTOHs and PFCAs at levels of 25 and 200 ng/mL or ng/g, ranged from 81 to 101%. Finally, the utility of the method was demonstrated by dosing male CD-1 mice with 30 mg/kg-BW of 8-2 fTOH and quantifying PFCs 6h post-treatment. The advantages of this method are (1) the simultaneous detection of both volatile and non-volatile fluorotelomer-based chemicals in complex matrices, such as mammalian tissues, (2) as a confirmatory method to LC-MS/MS, and (3) as an alternative method of analysis for laboratories without access to LC-MS/MS.

QSAR study of the reduction of nitroaromatics by Fe(II) species.

The development of predictive models for the reductive transformation of nitroaromatics requires further clarification of the effect of environmentally relevant variables on reaction kinetics and the identification of readily available molecular descriptors for calculating reactivity. Toward these goals, studies were performed on the reduction of a series of monosubstituted nitrobenzenes in Fe(II)-treated goethite suspensions. The energy of the lowest unoccupied molecular orbital, ELUMO (B3LYP/6-31G*,water), of the nitrobenzenes was capable of explaining 99% of the variability in the rates. Results of experiments in which the surface area loading of ferric oxides was systematically varied indicate that (i) the reactivity of mineral-surface-associated Fe(II), Fe(II)surf, toward the reduction of p-cyanonitrobenzene (CNNB) decreased in the order hematite > goethite > lepidocrocite > ferrihydrite and (ii) the surface density of Fe(II)surf did not play a crucial role in determining the observed reactivity trend. CNNB was reduced in Fe(II)-only control experiments in a pH range of 7.28-7.97 with a pH dependency consistent with the transformation of Fe(II) to Fe(OH)3 or related oxides. The pH dependency of the reduction of CNNB in Fe(II)-treated ferric oxide suspensions (pH 6.1-7.97) could be accounted for by the oxidation of Fe(II)surf, forming an Fe(III) oxide.

Reduction of nitrosobenzenes and N-hydroxylanilines by Fe(II) species: elucidation of the reaction mechanism.

Although there has been a substantial effort toward understanding the reduction of nitroaromatics in Fe(II)-treated ferric oxide systems, little has been done to gain insight into the factors controlling the transformation of their reaction intermediates, nitrosobenzenes and N-hydroxylanilines, in such systems. Nitrosobenzenes, the first intermediates, were reduced by Fe(II) solutions as well as by Fe(II)-treated goethite suspensions at pH 6.6. Experimental observations indicate a reactivitytrend in which the presence of electron-withdrawing groups in the para position increased the rate of reduction of the nitrosobenzenes. N-Hydroxylanilines, the second intermediates, were reduced in Fe(II)-treated goethite suspensions but were not reduced by Fe(II)aq. Their reactivity trend indicates that electron-withdrawing groups in the para position decreased their rate of reduction. The bond dissociation enthalpy of the N-O linkage was the most useful molecular descriptor for predicting the rates of reduction of N-hydroxylanilines in Fe(II)-treated goethite suspensions, suggesting that the cleavage of the N-O bond is the rate-determining step for reduction. The rate of reduction of p-cyano-N-hydroxylaniline showed a linear relationship against the concentration of surface-associated Fe(II) in hematite, goethite, and lepidocrocite suspensions, while having a relatively low sensitivity toward changes in pH within the near-neutral range in hematite suspensions.

Nitroaromatic reduction kinetics as a function of dominant terminal electron acceptor processes in natural sediments.

The reductive transformation of p-cyanonitrobenzene (pCNB) was investigated in laboratory batch slurries exhibiting dominant terminal electron accepting processes (TEAPs). Pseudo-first-order rate constants (k(obs)) were measured for the reduction of pCNB in nitrate-reducing, iron-reducing, sulfate-reducing, and methanogenic sediment slurries. Reduction was extremely slow in nitrate-reducing slurries but increased in slurries exhibiting TEAPs with significant concentrations of solution phase Fe(ll). As the reduction of pCNB progressed in the Fe(ll) rich systems, significant but nonstoichiometric decreases in aqueous Fe(ll) concentration were measured. Normalization of k(obs) to initial aqueous Fe(ll) concentrations (k(obs)/[Fe(ll)]t=0) gave values ranging from 0.0040 to 0.0052 d(-1) microM(-1) for nitrate-reducing, iron-reducing, and methanogenic sediment slurries as well as sulfate-reducing sediment slurries in which lactate served as a source of organic carbon. The k(obs)/ [Fe(ll)]t=0 ratios were 1-fold greater for sulfate-reducing batch slurries amended with acetate and iron-reducing slurries equilibrated with a 3% H2 atmosphere indicating that the electron source and system parameters such as pH play a determinant role in the reaction kinetics. Although these data demonstrate that aqueous phase Fe(ll) must be present for significant reduction to occur, a limited role for aqueous phase Fe(ll) as a quantitative indicator of reactivity is suggested.