Matt F. Simcik

Analytical challenges hamper perfluoroalkyl research

The growing concern over these organohalogens, some of which have been found in human blood and appear to be widespread in the environment, led researchers to gather in Hamburg, Germany, in 2003 to evaluate the current state of methods to analyze for the organic contaminants. Jonathan Martin of the University of Toronto and 20 colleagues from industry, government, and academia summarize the main recommendations from the workshop.

Mechanisms for removal of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) from drinking water by conventional and enhanced coagulation

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are persistent organic pollutants that have been found to be ubiquitous in the environment. This article, for the first time, delineates removal areas of these polar compounds on a coagulation diagram that associates chemical conditions with different coagulation mechanisms. Variables considered were solution pH, coagulant dosage, coagulants (alum and ferric chloride), natural organic matter (NOM), initial turbidity, and flocculation time. The jar-test results show that conventional coagulation (alum dosage of 10-60 mg/L and final pH of 6.5-8.0) removed ≤20% of PFOS and PFOA. These chemicals tended to be removed better by enhanced coagulation at higher coagulant dosages (>60 mg/L) and (thus) lower final pH (4.5-6.5). A coagulation diagram was developed to define the coagulant dosage and solution pH for PFOS/PFOA removal. The results suggest that the primary PFOS/PFOA removal mechanism is adsorption to fine Al hydroxide flocs freshly formed during the initial stage of coagulation; increasing flocculation time from 2 to 90 min could not further improve PFOS and PFOA removals. Furthermore, the effect of NOM on PFOS/PFOA removal by coagulation was examined, and possible removal mechanisms were discussed.

Input characterization of perfluoroalkyl substances in wastewater treatment plants: Source discrimination by exploratory data analysis

This paper presents a methodology based on multivariate data analysis for identifying input sources of perfluoroalkyl substances (PFASs) detected in 37 wastewater treatment plants (WWTPs) across more than 40 cities in the state of Minnesota (USA). Exploratory analysis of data points has been carried out by unsupervised pattern recognition (cluster analysis), correlation analysis, ANOVA and per capita discharges in an attempt to discriminate sources of PFASs in WWTPs. Robust cluster solutions grouped the database according to the different PFAS profiles in WWTP influent. Significantly elevated levels of perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA) and/or perfluorooctane sulfonate (PFOS) in influent have been found in 18 out of 37 WWTPs (49%). A substantial increase in the concentrations of PFHxA and/or PFOA from influent to effluent was observed in 59% of the WWTPs surveyed, suggestive of high concentration inputs of precursors. The fate of one precursor (8:2 fluorotelomer alcohol) in WWTP was modeled based on fugacity analysis to understand the increasing effluent concentration. Furthermore, population-related emissions cannot wholly explain the occurrence and levels of PFASs in WWTPs. Unusually high influent levels of PFASs were observed in WWTPs located in specific industrial areas or where known contamination had taken place. Despite the restriction on the production/use of PFOA and PFOS, this paper demonstrates that wastewater from industrial activities is still a principal determinant of PFAS pollution in urban watersheds.

Effects of monovalent cations on the competitive adsorption of perfluoroalkyl acids by kaolinite: Experimental studies and modeling

Our hypothesis that longer-chained perfluoroalkyl acids (PFAAs) outcompete shorter-chained PFAAs during adsorption was tested in this study, wherein the adsorption interactions of six frequently detected PFAAs with kaolinite clay were modeled and examined experimentally using various suspension compositions. Competitive adsorption of PFAAs on the kaolinite surface was observed for the first time, and longer-chained PFAAs outcompeted those with a shorter chain. The electrostatic repulsion between adsorbed PFAA molecules is a primary inhibitory factor in PFAA adsorption. An increase in aqueous sodium or hydrogen ion concentration weakened electrostatic repulsions and changed the adsorption free energy. Therefore, the adsorption of a shorter-chained PFAA with weaker hydrophobicity could occur at high sodium or hydrogen ion concentrations. The experimental and modeling data suggest that the adsorption of shorter-chained PFAAs (≤4 perfluorinated carbons) in freshwater with a typical ionic strength of 10(-2.5) is not thermodynamically favorable. Furthermore, by measuring the electrokinetic potential of kaolinite suspension in the presence of PFAAs, we found that the kaolinite surface became more negatively charged because of the adsorption of PFAAs. This observation indicates that the adsorbed PFAA molecules were within the electrical double layer of the kaolinite surface and that they contributed to the potential at the slipping plane. The possible alignments of adsorbed PFAA molecules on the kaolinite surface were then proposed.

Occurrence and fate of the herbicide glyphosate and its degradate aminomethylphosphonic acid in the atmosphere

This is the first report on the ambient levels of glyphosate, the most widely used herbicide in the United States, and its major degradation product, aminomethylphosphonic acid (AMPA), in air and rain. Concurrent, weekly integrated air particle and rain samples were collected during two growing seasons in agricultural areas in Mississippi and Iowa. Rain was also collected in Indiana in a preliminary phase of the study. The frequency of glyphosate detection ranged from 60 to 100% in both air and rain. The concentrations of glyphosate ranged from <0.01 to 9.1 ng/m(3) and from <0.1 to 2.5 µg/L in air and rain samples, respectively. The frequency of detection and median and maximum concentrations of glyphosate in air were similar or greater to those of the other high-use herbicides observed in the Mississippi River basin, whereas its concentration in rain was greater than the other herbicides. It is not known what percentage of the applied glyphosate is introduced into the air, but it was estimated that up to 0.7% of application is removed from the air in rainfall. Glyphosate is efficiently removed from the air; it is estimated that an average of 97% of the glyphosate in the air is removed by a weekly rainfall ≥ 30 mm.

Perfluoroalkyl acids in urban stormwater runoff: influence of land use.

Perfluoroalkyl acids (PFAAs) are persistent organic pollutants in the environment and have been reported to have nonpoint sources. In this study, six PFAAs with different chain lengths were monitored in stormwater runoff from seven storm events (2009-2011) at various outfall locations corresponding to different watershed land uses. We found PFAA(s) in 100% of stormwater runoff samples. Monitoring results and statistical analysis show that PFAAs in stormwater runoff from residential areas mainly came from rainfall. On the other hand, non-atmospheric sources at both industrial and commercial areas contributed PFAAs in stormwater runoff. The mass flux of PFAAs from stormwater runoff in the Twin Cities (Minneapolis and St. Paul, MN) metropolitan area is estimated to be about 7.86 kg/year. In addition, for the first time, we monitored PFAAs on the particles/debris in stormwater runoff and found high-level PFOS on the particulate matter in runoff collected from both industrial and commercial areas; the levels were so high that the finding could not be explained by the solid-water partitioning or adsorption. PFOS on the particulate matter is suspected to have originated from industrial/commercial products, entering the waste stream as PFOS containing particles.

Peer Reviewed: Analytical Challenges Hamper Perfluoroalkyl Research

The growing concern over these organohalogens, some of which have been found in human blood and appear to be widespread in the environment, led researchers to gather in Hamburg, Germany, in 2003 to evaluate the current state of methods to analyze for the organic contaminants. Jonathan Martin of the University of Toronto and 20 colleagues from industry, government, and academia summarize the main recommendations from the workshop.

A Comparison of Mercury Cycling in Lakes Michigan and Superior

ABSTRACT Mercury cycling in Lake Superior and Lake Michigan was evaluated based on measurements of mercury levels, modeling of evasional fluxes, and development of first-order mass balance models. Total mercury, methylmercury, and dissolved gaseous mercury were measured on sampling cruises in Lake Michigan (2005) and Lake Superior (2006). Average total mercury concentrations in unfiltered surface water were higher in Lake Michigan (420 ± 40 pg/L) compared to Lake Superior (210 ± 20 pg/L). Methylmercury levels were below the detection limit in Lake Michigan. Larger sample volumes were collected to lower detection limits in Lake Superior in 2006 and methylmercury levels averaged 7 ± 6 pg/L. Dissolved gaseous mercury concentrations were also higher in Lake Michigan (27 ± 7 pg/L) compared to Lake Superior (14 ± 8 pg/L). Evasional fluxes were estimated using a two-film model for air-water exchange. The annual evasional flux in Lake Michigan was determined to be ∼380 kg/yr from Lake Michigan and ∼160 kg/yr from Lake Superior. Total mercury burdens in each lake were estimated to be ∼2500 kg in Superior and ∼2100 kg in Lake Michigan demonstrating that evasional fluxes play an important role in the mass balance of each lake, particularly Lake Michigan. A simple first-order mass balance model demonstrates the importance of air-water exchange and sedimentation as primary removal processes for Hg in each lake. Uncertainties in the mass balance model are highlighted due to lack of key data, particularly in Lake Superior.

Predicting aqueous solubility of environmentally relevant compounds from molecular features: A simple but highly effective four-dimensional model based on Project to Latent Structures

The aqueous solubility (log S) of xenobiotic chemicals has been identified as a key characteristic in determining their bioaccessibility/bioavailability and their fate and transport in aquatic environments. We here explore and evaluate the use of a state-of-the-art data analysis technique (Project to Latent Structures, PLS) to estimate log S of environmentally relevant chemicals. A large number (n = 624) of molecular descriptors was computed for over 1400 organic chemicals, and then refined by a feature selection technique. Candidate predictor descriptors were fitted to data by means of PLS, which was optimized by an internal leave-one-out cross-validation technique and validated by an external data set. The final (best) PLS model with only four variables (AlogP, X1sol, Mv, and E) exhibited noteworthy stability and good predictive power. It was able to explain 91% of the data (n = 1400) variance with an average absolute error of 0.5 log units through the solubilities span over 12 orders of magnitude. The newly proposed model is transparent, easily portable from one user to another, and robust enough to accurately estimate log S of a wide range of emerging contaminants.

Perfluorooctane sulfonate (PFOS) contamination of fish in urban lakes: a prioritization methodology for lake management.

The contamination of urban lakes by anthropogenic pollutants such as perfluorooctane sulfonate (PFOS) is a worldwide environmental problem. Large-scale, long-term monitoring of urban lakes requires careful prioritization of available resources, focusing efforts on potentially impaired lakes. Herein, a database of PFOS concentrations in 304 fish caught from 28 urban lakes was used for development of an urban-lake prioritization framework by means of exploratory data analysis (EDA) with the aid of a geographical information system. The prioritization scheme consists of three main tiers: preliminary classification, carried out by hierarchical cluster analysis; predictor screening, fulfilled by a regression tree method; and model development by means of a neural network. The predictive performance of the newly developed model was assessed using a training/validation splitting method and determined by an external validation set. The application of the model in the U.S. state of Minnesota identified 40 urban lakes that may contain elevated levels of PFOS; these lakes were not previously considered in PFOS monitoring programs. The model results also highlight ongoing industrial/commercial activities as a principal determinant of PFOS pollution in urban lakes, and suggest vehicular traffic as an important source and surface runoff as a primary pollution carrier. In addition, the EDA approach was further compared to a spatial interpolation method (kriging), and their advantages and disadvantages were discussed.