The review examines literature relevant to environmental fate, transformation, and toxicity, and human exposure and health risks of neonicotinoid insecticides.

Widespread use of perfluorooctane surfactants has led to ubiquitous presence of these chemicals in biological tissues. While perfluorooctane surfactants have been measured in blood and liver tissue samples of fish, birds, and mammals in the Great Lakes region, data for the aqueous concentrations of these compounds in the Great Lakes or other ambient waters is lacking. Sixteen Great Lakes water samples were analyzed for eight perfluorooctane surfactants. The monitored perfluorooctane surfactants were quantitatively determined using single quadrupole HPLC/MS and qualitatively confirmed using ion trap MS/MS. Additionally, PFOS was quantitatively confirmed using triple quadrupole LC/MS/MS. Concentrations of PFOS and PFOA in the two lakes ranged from 21-70 and 27-50 ng/L, respectively. Analysis also showed the presence of PFOS precursors, N-EtFOSAA (range of 4.2-11 ng/L) and FOSA (range of 0.6-1.3 ng/L), in all samples above the LOQ. PFOSulfinate, another precursor, was identified at six of eight locations with a concentration range, when present, of <2.2-17 ng/L. Other PFOS precursors, N-EtFOSE, PFOSAA, and N-EtFOSA were not observed at any of the sampling locations. These are the first reported concentrations of perfluorooctane surfactants in Great Lakes water and the first report of PFOS precursors in any water body.

The origin and amount of perfluorooctane surfactants in wastewater treatment systems, and the transformation these compounds may undergo during treatment, were evaluated through measurement and experiment. Influent, effluent, and river water at the point of discharge for a 6-MGD wastewater treatment plant (WWTP) were screened for eight perfluorooctane surfactants. N-EtFOSAA was quantified in influent (5.1 +/- 0.8 ng/L), effluent (3.6 +/- 0.2 ng/ L), and river water samples (1.2 +/- 0.3 ng/L), while PFOS and PFOA were quantified in effluent (26 +/- 2.0 and 22 +/- 2.1 ng/L, respectively) and river water (23 +/- 1.5 and 8.7 +/- 0.8 ng/L, respectively). Signals for PFOS and PFOA were observed in influent samples, but exact quantitative determination could not be made due to low recoveries of these two compounds in field spike samples. Although the source of PFOS and PFOA observed in WWTP effluents is not clear, two hypotheses were examined: (1) the highly substituted perfluorooctane surfactants that constitute commercially available fabric protectors can be transformed to PFOS and PFOA during biological treatment in wastewater treatment systems, and (2) the end products themselves are directly introduced to WWTPs because they are present as residual in the commercial mixtures. Biotransformation experiments of 96 h were run to determine whether N-EtFOSE (a primary monomer used in 3M's polymer surface protection products) could be transformed to lesser-substituted perfluorooctane compounds in bioreactors amended with aerobic and anaerobic sludge from the sampled plant. At the end of the aerobic biotransformation experiment, N-EtFOSAA and PFOSulfinate were the only two metabolites formed and each accounted for 23 +/- 5.0% and 5.3 +/- 0.8% of the transformed parent on a molar basis, respectively. Transformation of N-EtFOSE was not observed under anaerobic conditions. A sample of a commercially available surface protection product from 1994 was analyzed and found to contain six of the targeted perfluorinated surfactants, including PFOS and PFOA. These findings suggest transformation of precursors within wastewater treatment is not an important source of these compounds compared to direct use and disposal of products containing the end products as residual amounts.

We developed an electrospun carbon nanofiber-carbon nanotube (CNF-CNT) composite with optimal sorption capacity and material strength for point-of-use (POU) water treatment. Synthesis variables including integration of multiwalled carbon nanotubes (CNTs) and macroporosity (via sublimation of phthalic acid), relative humidity (20 and 40%), and stabilization temperature (250 and 280 °C) were used to control nanofiber diameter and surface area (from electron microscopy and BET isotherms, respectively), surface composition (from XPS), and strength (from AFM nanoindentation and tensile strength tests). Composites were then evaluated using kinetic, isotherm, and pH-edge sorption experiments with sulfamethoxazole (log Kow = 0.89) and atrazine (log Kow = 2.61), representative micropollutants chosen for their different polarities. Although CNFs alone were poor sorbents, integration of CNTs and macroporosity achieved uptake comparable to granular activated carbon. Through reactivity comparisons with CNT dispersions, we propose that increasing macroporosity exposes the embedded CNTs, thereby enabling their role as the primary sorbent in nanofiber composites. Because the highest capacity sorbents lacked sufficient strength, our optimal formulation (polyacrylonitrile 8 wt %, CNT 2 wt %, phthalic acid 2.4 wt %; 40% relative humidity; 280 °C stabilization) represents a compromise between strength and performance. This optimized sorbent was tested with a mixture of ten organic micropollutants at environmentally relevant concentrations in a gravity-fed, flow-through filtration system, where removal trends suggest that both hydrophobic and specific binding interactions contribute to micropollutant uptake. Collectively, this work highlights the promise of CNF-CNT filters (e.g., mechanical strength, ability to harness CNT sorption capacity), while also prioritizing areas for future research and development (e.g., improved removal of highly polar micropollutants, sensitivity to interfering cosolutes).

A Good Laboratory Practices (GLP) validated, multiresidue analytical method is presented for the determination of the chloroacetanilide herbicides metolachlor, acetochlor, and alachlor, the chloroacetamide herbicide dimethenamid, and their respective ethanesulfonic (ESA) and oxanillic (OA) acid degradates in ground and surface water. A 50-mL water sample is subjected to purification using a C-18 SPE column. The four parent components and their eight ESA and OA degradates are isolated using 80/20 methanol/water (v/v) for elution. The eluate is reduced to < 1.0 mL and reconstituted in 10/90 acetonitrile/water (v/v) to the desired final fraction volume. Final analysis is accomplished using liquid chromatography/electrospray ionization-mass spectrometry/mass spectrometry in the + (parent compounds) and - (ESA and OA degradates) ion modes by monitoring appropriate precursor/product ion pairs for each of the 12 analytes. The method limit of quantification is 0.10 ppb and the limit of detection is 0.125 ng injected for each analyte. Average procedural recovery data range from 95 to 105% for fortification levels of 0.10-100 ppb. The method validation study was performed following GLP guidelines.

Alkylated perfluorooctanesulfonamides are compounds of environmental concern. To make these compounds available for environmental and toxicological studies, a series of N-alkylated perfluorooctanesulfonamides and structurally related compounds were synthesized by reaction of the corresponding perfluoroalkanesulfonyl fluoride with a suitable primary or secondary amine. Perfluoroalkanesulfonamidoethanols were obtained from the N-alkyl perfluoroalkanesulfonamides either by direct alkylation with bromoethanol or alkylation with acetic acid 2-bromo-ethyl ester followed by hydrolysis of the acetate. N-Alkyl perfluorooctanesulfonamidoacetates were synthesized in an analogous way by alkylation of N-alkyl perfluoroalkanesulfonamides with a bromo acetic acid ester, followed by basic ester hydrolysis. Alternatively, N-alkyl perfluoroalkanesulfonamides can be alkylated with an appropriate alcohol using the Mitsunobu reaction. Perfluorooctanesulfonamide was synthesized from the perfluorooctanesulfonyl fluoride via the azide by reduction with Zn/HCl. All perfluorooctanesulfonamides contained linear as well as branched C 8 F 17 isomers, typically in a 20:1 to 30:1 ratio. The crystal structures of N-ethyl and N,N-diethyl perfluorooctanesulfonamide show that the S-N bond has considerable double bond character. This double bond character results in a significant rotational barrier around the S-N bond (ΔG ≠ = 62-71 kJ mol −1 ) and a preferred solid state and solution conformation in which the N-alkyl groups are oriented opposite to the perfluorooctyl group to minimize steric crowding around the S-N bond.

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This work was supported by a grand-in-aid from the Toyota Foundation (No.82-1-III-031) and the Ministry of Education of Japan (No.