Atmospheric chemistry of n-C(x)F(2)(x)(+1)CHO (x = 1, 2, 3, 4): fate of n-C(x)F(2)(x)(+1)C(O) radicals.

Smog chamber/FTIR techniques were used to study the atmospheric fate of n-C(x)F(2)(x)(+1)C(O) (x = 1, 2, 3, 4) radicals in 700 Torr O(2)/N(2) diluent at 298 +/- 3 K. A competition is observed between reaction with O(2) to form n-C(x)()F(2)(x)()(+1)C(O)O(2) radicals and decomposition to form n-C(x)F(2)(x)(+1) radicals and CO. In 700 Torr O(2)/N(2) diluent at 298 +/- 3 K, the rate constant ratio, k(n-C(x)F(2)(x)(+1)C(O) + O(2) --> n-C(x)F(2)(x)(+1)C(O)O(2))/k(n-C(x)F(2)(x)(+1)C(O) --> n-C(x)F(2)(x)(+1) + CO) = (1.30 +/- 0.05) x 10(-17), (1.90 +/- 0.17) x 10(-19), (5.04 +/- 0.40) x 10(-20), and (2.67 +/- 0.42) x 10(-20) cm(3) molecule(-1) for x = 1, 2, 3, 4, respectively. In one atmosphere of air at 298 K, reaction with O(2) accounts for 99%, 50%, 21%, and 12% of the loss of n-C(x)F(2)(x)(+1)C(O) radicals for x = 1, 2, 3, 4, respectively. Results are discussed with respect to the atmospheric chemistry of n-C(x)F(2)(x)(+1)C(O) radicals and their possible role in contributing to the formation of perfluorocarboxylic acids in the environment.

Atmospheric chemistry of perfluorinated aldehyde hydrates (n-C(x)F(2x+1)CH(OH)2, x = 1, 3, 4): hydration, dehydration, and kinetics and mechanism of Cl atom and OH radical initiated oxidation.

Smog chamber/Fourier transform infrared (FTIR) techniques were used to measure k(Cl+C(x)F(2x+1)CH(OH)(2)) (x = 1, 3, 4) = (5.84 +/- 0.92) x 10(-13) and k(OH+C(x)F(2x+1)CH(OH)(2)) = (1.22 +/- 0.26) x 10(-13) cm(3) molecule(-1) s(-1) in 700 Torr of N(2) or air at 296 +/- 2 K. The Cl initiated oxidation of CF(3)CH(OH)(2) in 700 Torr of air gave CF(3)COOH in a molar yield of 101 +/- 6%. IR spectra of C(x)F(2x+1)CH(OH)(2) (x = 1, 3, 4) were recorded and are presented. An upper limit of k(CF(3)CHO+H(2)O) < 2 x 10(-23) cm(3) molecule(-1) s(-1) was established for the gas-phase hydration of CF(3)CHO. Bubbling CF(3)CHO/air mixtures through liquid water led to >80% conversion of CF(3)CHO into the hydrate within the approximately 2 s taken for passage through the bubbler. These results suggest that OH radical initiated oxidation of C(x)F(2x+1)CH(OH)(2) hydrates could be a significant source of perfluorinated carboxylic acids in the environment.

Atmospheric chemistry of perfluoroalkanesulfonamides: kinetic and product studies of the OH radical and Cl atom initiated oxidation of N-ethyl perfluorobutanesulfonamide.

Perfluorooctanesulfonamides [C8F17SO2N(R1)(R2)] are present in the atmosphere and may, via atmospheric transport and oxidation, contribute to perfluorocarboxylates (PFCA) and perfluorooctanesulfonate (PFOS) pollution in remote locations. Smog chamber experiments with the perfluorobutanesulfonyl analogue N-ethyl perfluorobutanesulfonamide [NEtFBSA; C4F9SO2N(H)CH2CH3] were performed to assess this possibility. By use of relative rate methods, rate constants for reactions of NEtFBSA with chlorine atoms (296 K) and OH radicals (301 K) were determined to be kCL) = (8.37 +/- 1.44) x 10(-12) and kOH = (3.74 +/- 0.77) x 10(-13) cm3 molecule(-1) s(-1), indicating OH reactions will be dominant in the troposphere. Simple modeling exercises suggestthat reaction with OH radicals will dominate removal of perfluoroalkanesulfonamides from the gas phase (wet and dry deposition will not be important) and that the atmospheric lifetime of NEtFBSA in the gas phase will be 20-50 days, thus allowing substantial long-range atmospheric transport. Liquid chromatography/tandem mass spectrometry (LC/MS/MS) analysis showed that the primary products of chlorine atom initiated oxidation were the ketone C4F9SO2N(H)COCH3; aldehyde 1, C4F9SO2N(H)CH2CHO; and a product identified as C4F9SO2N(C2H5O)- by high-resolution MS but whose structure remains tentative. Another reaction product, aldehyde 2, C4F9SO2N(H)CHO, was also observed and was presumed to be a secondary oxidation product of aldehyde 1. Perfluorobutanesulfonate was not detected above the level of the blank in any sample; however, three perfluoroalkanecarboxylates (C3F7CO2-, C2F5CO2-, and CF3CO2-) were detected in all samples. Taken together, results suggest a plausible route by which perfluorooctanesulfonamides may serve as atmospheric sources of PFCAs, including perfluorooctanoic acid.

Formation of C7F15COOH (PFOA) and other perfluorocarboxylic acids during the atmospheric oxidation of 8:2 fluorotelomer alcohol.

Calculations using a three-dimensional global atmospheric chemistry model (IMPACT) indicate that n-C8F17CH2CH2OH (widely used in industrial and consumer products) degrades in the atmosphere to give perfluorooctanoic acid (PFOA) and other perfluorocarboxylic acids (PFCAs). PFOA is persistent, bioaccumulative, and potentially toxic. Molar yields of PFOA depend on location and season, are in the range of 1-10%, and are of the correct order of magnitude to explain the observed levels in Arctic fauna. Fluorotelomer alcohols such as n-C8F17CH2CH2OH appear to be a significant global source of persistent bioaccumulative perfluorocarboxylic acid pollution. This is the first modeling study of the atmospheric chemistry of a fluorotelomer alcohol.

Microcosm evaluation of the toxicity and risk to aquatic macrophytes from perfluorooctane sulfonic acid.

Perfluorooctane sulfonic acid (PFOS) is an anthropogenic contaminant detected in various environmental and biologic matrices. This compound is a fluorinated surfactant, a class of molecules renowned for their persistence and their global distribution but for which few ecotoxicological data are currently available, especially under field conditions. The toxicity of PFOS to the aquatic macrophytes Myriophyllum sibiricum and M. spicatum was investigated using 12,000 L outdoor microcosms. Replicate microcosms (n = 3) were treated with 0.3, 3, 10, and 30 mg/L PFOS as the potassium salt and assessed at regular intervals during a period of 42 days. M. sibiricum was more sensitive to PFOS under these simulated field conditions than M. spicatum. Toxicity was observed in the evaluated end points at > 3 mg/L PFOS for EC10s and > 12 mg/L PFOS for EC50s for M. spicatum and in M. sibiricum at > 0.1 mg/L PFOS for EC10s and > 1.6 mg/L PFOS for EC50s. The no observed-effect concentration (NOEC) for M. spicatum was consistently > or = 11.4 mg/L PFOS, whereas the NOEC for M. sibiricum was > or = 0.3 mg/L PFOS. A risk assessment for these plants estimated a negligible probability of toxicity being observed in these plants from PFOS exposure at current environmental concentrations.

Atmospheric chemistry of CF3CH2CH2OH: kinetics, mechanisms and products of Cl atom and OH radical initiated oxidation in the presence and absence of NOX.

Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with CF(3)CH(2)C(O)H and CF(3)CH(2)CH(2)OH in 700 Torr of N(2) or air diluent at 296 +/- 2 K. The rate constants determined were k(Cl+CF(3)CH(2)C(O)H) = (1.81 +/- 0.27) x 10(-11), k(OH+CF(3)CH(2)C(O)H) = (2.57 +/- 0.44) x 10(-12), k(Cl+CF(3)CH(2)CH(2)OH) = (1.59 +/- 0.20) x 10(-11), and k(OH+CF(3)CH(2)CH(2)OH) = (6.91 +/- 0.91) x 10(-13) cm(3) molecule(-1) s(-1). Product studies of the chlorine initiated oxidation of CF(3)CH(2)CH(2)OH in the absence of NO show the sole primary product to be CF(3)CH(2)C(O)H. Product studies of the chlorine initiated oxidation of CF(3)CH(2)CH(2)OH in the presence of NO show the primary products to be CF(3)CH(2)C(O)H (81%), HC(O)OH (10%), and CF(3)C(O)H. Product studies of the chlorine initiated oxidation of CF(3)CH(2)C(O)H in the absence of NO show the primary products to be CF(3)C(O)H (76%), CF(3)CH(2)C(O)OH (14%), and CF(3)CH(2)C(O)OOH (< or =10%). As part of this work, an upper limit of k(O(3)+CF(3)CH(2)CH(2)OH) < 2 x 10(-21) cm(3) molecule(-1) s(-1) was established. Results are discussed with respect to the atmospheric chemistry of fluorinated alcohols.

Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C4F9CH2CH2OH): products and mechanism of Cl atom initiated oxidation in the presence of NOx.

Smog chamber/FTIR techniques were used to study the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (C(4)F(9)CH(2)CH(2)OH, 4:2 FTOH) in the presence of NO(x) in 700 Torr of N(2)/O(2) diluent at 296 K. Chemical activation effects play an important role in the atmospheric chemistry of the peroxy, and possibly the alkoxy, radicals derived from 4:2 FTOH. Cl atoms react with C(4)F(9)CH(2)CH(2)OH to give C(4)F(9)CH(2)C(*)HOH radicals which add O(2) to give chemically activated alpha-hydroxyperoxy radicals, [C(4)F(9)CH(2)C(OO(*))HOH]*. In 700 Torr of N(2)/O(2) at 296 K, approximately 50% of the [C(4)F(9)CH(2)C(OO(*))HOH]* radicals decompose "promptly" to give HO(2) radicals and C(4)F(9)CH(2)CHO, the remaining [C(4)F(9)CH(2)C(OO(*))HOH]* radicals undergo collisional deactivation to give thermalized peroxy radicals, C(4)F(9)CH(2)C(OO(*))HOH. Decomposition to HO(2) and C(4)F(9)CH(2)CHO is the dominant atmospheric fate of the thermalized peroxy radicals. In the presence of excess NO, the thermalized peroxy radicals react to give C(4)F(9)CH(2)C(O(*))HOH radicals which then decompose at a rate >2.5 x 10(6) s(-1) to give HC(O)OH and the alkyl radical C(4)F(9)CH(2)(*). The primary products of 4:2 FTOH oxidation in the presence of excess NO(x) are C(4)F(9)CH(2)CHO, C(4)F(9)CHO, and HCOOH. Secondary products include C(4)F(9)CH(2)C(O)O(2)NO(2), C(4)F(9)C(O)O(2)NO(2), and COF(2). In contrast to experiments conducted in the absence of NO(x), there was no evidence (<2% yield) for the formation of the perfluorinated acid C(4)F(9)C(O)OH. The results are discussed with regard to the atmospheric chemistry of fluorotelomer alcohols.

Atmospheric lifetime of fluorotelomer alcohols.

Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with a series of fluorotelomer alcohols, F(CF2CF2)nCH2CH2OH (n = 2, 3, 4), in 700 Torr of N2 or air, diluent at 296 +/- 2K. The length of the F(CF2CF2)n- group had no discernible impact on the reactivity of the molecule. For n = 2, 3, or 4, k(Cl + F(CF2CF2)nCH2CH2OH) = (1.61 +/- 0.49) x 10(-11) and k(OH + F(CF2CF2)nCH2CH2OH) = (1.07 +/- 0.22) x 10(-12) cm3 molecule(-1) s(-1). Consideration of the likely rates of other possible atmospheric loss mechanisms leads to the conclusion that the atmospheric lifetime of F(CF2CF2)nCH2CH2OH (n > or = 2) is determined by reaction with OH radicals and is approximately 20 d.

Laboratory evaluation of the toxicity of Perfluorooctane Sulfonate (PFOS) on Selenastrum capricornutum, Chlorella vulgaris, Lemna gibba, Daphnia magna, and Daphnia pulicaria.

Perfluorooctane sulfonate (PFOS) is an anthropogenic compound found in trace amounts in many environmental compartments far from areas of production. This, along with the highly persistent nature of PFOS, presents a concern for possible effects in aquatic ecosystems. The objective of this study was to determine the toxicity of PFOS in representative freshwater organisms. Toxicity testing using standard laboratory protocols was performed on the green algae Selenastrum capricornutum and Chlorella vulgaris, the floating macrophyte Lemna gibba, and the invertebrates Daphnia magna and Daphnia pulicaria. No observable effect concentration (NOEC) values were generated from the most sensitive endpoints for all organisms. Autotroph inhibition of growth NOEC values were 5.3, 8.2, and 6.6 mg/L for S. capricornutum, C. vulgaris, and L. gibba, respectively. The 48-h immobility NOEC values for D. magna and D. pulicaria were 0.8 and 13.6 mg/L, respectively. In comparison to immobility, the 21-day lethality NOEC for D. magna was 5.3 mg/L. Based on effect (immobility) values, the most sensitive of all test organisms was D. magna. The most sensitive organism based on 50% inhibition of growth (IC(50)) was L. gibba, with an IC(50) value of 31.1 mg/L determined from wet weight. This is 4.3 times less than the LC(50) for D. pulicaria, which was 134 mg/L. Significant adverse effects (p < or = 0.05) were observed for all organisms in concentrations >134 mg/L. The results indicate that under laboratory conditions PFOS is acutely toxic to freshwater organisms at concentrations at or near 100 mg/L. Based on known environmental concentrations of PFOS, which occur in the low ng/L to low microg/L range, there is no apparent risk to freshwater systems. However, further work is required to investigate long-term effects in these and other freshwater organisms.

Thermolysis of fluoropolymers as a potential source of halogenated organic acids in the environment.

Following the introduction of hydrochlorofluorocarbon (HCFCs) and hydrofluorocarbon (HFCs) gases as replacements for the ozone-destroying chlorofluorocarbons (CFCs), it has been discovered that HCFCs/HFCs can degrade in the atmosphere to produce trifluoroacetic acid, a compound with no known loss mechanisms in the environment, and higher concentrations in natural waters have been shown to be mildly phytotoxic. Present environmental levels of trifluooracetic acid are not accounted by HCFC/HFC degradation alone. Here we report that thermolysis of fluorinated polymers, such as the commercial polymers Teflon and Kel-F, can also produce trifluoroacetate and the similar compound chlorodifluoroacetate. This can occur either directly, or indirectly via products that are known to degrade to these haloacetates in the atmosphere. The environmental significance of these findings is confirmed by modelling, which indicates that the thermolysis of fluoropolymers in industrial and consumer high-temperature applications (ovens, non-stick cooking utensils and combustion engines) is likely to be a significant source of trifluoroacetate in urban rain water ( approximately 25 ng l-1, as estimated for Toronto). Thermolysis also leads to longer chain polyfluoro- and/or polychlorofluoro- (C3-C14) carboxylic acids which may be equally persistent. Some of these products have recently been linked with possible adverse health and environmental impacts and are being phased out of the US market. Furthermore, we detected CFCs and fluorocarbons-groups that can destroy ozone and act as greenhouse gases, respectively-among the other thermal degradation products, suggesting that continued use of fluoropolymers may also exacerbate stratospheric ozone-depletion and global warming.

Determination of perfluorinated surfactants in surface water samples by two independent analytical techniques: liquid chromatography/tandem mass spectrometry and 19F NMR.

Perfluorinated surfactants are an important class of specialty chemicals that have received recent attention as a result of their persistence in the environment. Two analytical methods for the determination of perfluorinated surfactants in aqueous samples were developed in order to investigate a spill of 22000 L of fire retardant foam containing perfluorinated surfactants into Etobicoke Creek (Toronto, Ontario). With the first method, aliquots of surface water (0.2-200 mL) were preconcentrated using solid-phase extraction. Liquid chromatography/tandem mass spectrometry was employed for identification and quantification of each perfluorinated surfactant. Total perfluorinated surfactant concentrations in surface water samples ranged from 0.011 to 2270 microg/L, and perfluorooctanesulfonate was the predominant surfactant observed. Interestingly, perfluorooctanoate was detected in surface water sampled upstream of the spill. A second method employing 19F NMR was developed for the determination of total perfluorinated surfactant concentrations in aqueous samples (2-100 mL). By 19F NMR, the surface water concentrations ranged from nondetect (method detection limit, 10 microg/L for a 100-mL sample) to 17000 microg/L. These methods permit comprehensive evaluation of aqueous samples for the presence of perfluorinated surfactants and have applicability to other sample matrixes.

The fate and persistence of trifluoroacetic and chloroacetic acids in pond waters.

The environmental fate of trichloro-, dichloro-, and monochloroacetic acids, and trifluoroacetic acid was investigated using field aquatic microcosms and laboratory sediment-water systems. Trifluoroacetic acid was extremely persistent and showed no degradation during a one-year field study, though it appeared to undergo transient partitioning within an unknown pond phase as the temperature of the surroundings was reduced. Of the three chloroacetic acids, trichloro had the longest residence time (induction and decay) (approximately 40 d), dichloro the shortest (approximately 4 d), and monochloro an intermediate residence time (approximately 14 d). Laboratory studies suggest that the biodegradation of trichloro-, dichloro-, and monochloroacetic acids leads primarily to the formation of chloride and oxalic, glyoxalic, and glycolic acids, respectively.

Chlorodifluoroacetic acid fate and toxicity to the macrophytes Lemna gibba, Myriophyllum spicatum, and Myriophyllum sibiricum in aquatic microcosms.

Chlorodifluoroacetic acid (CDFA) is a novel haloacetic acid (HAA) and has been recently documented in aquatic systems. It is a suspected degradation product of the refrigerants 1,1,2-trichloro-1,1-difluoroethane (CFC-113) and 1-chloro-1,1-difluoroethane (HCFC-142b). Haloacetic acids can be phytotoxic, putatively acting through inhibition of the citric acid cycle. Replicate (n = 3) 12,000-L model aquatic ecosystems (microcosms) were dosed once at 0.5, 1, 5, and 20 mg/L of neutralized CDFA. Three microcosms served as controls. Each microcosm was stocked with eight individual apical shoots of both Myriophyllum spicatum and Myriophyllum sibiricum and sampled at regular intervals over a 42-d exposure period. The plants were assessed for the somatic endpoints of plant length, root growth, node number, and wet and dry mass and the biochemical endpoints of chlorophyll-a/b and carotenoid content as well as citric acid levels. The duckweed Lemna gibba was also introduced into these systems and monitored over a period of 14 d for wet/dry mass, plant/frond number, chlorophyll content, and growth rate. Concentrations of CDFA remained constant in the water column over the course of the fate investigation (241 d), indicating that this compound undergoes little, if any, degradation in aquatic systems. Results showed few statistically significant differences from controls for all three plant species with exposure to CDFA but no biologically relevant impacts. Overall, CDFA does not appear to pose any risk to these aquatic macrophytes at current environmental concentrations.

The role of carbonate radical in limiting the persistence of sulfur-containing chemicals in sunlit natural waters.

Carbonate radical (*CO3-) is a selective oxidant that may be important in limiting the persistence of a number of sulfur-containing compounds in sunlit natural waters. Thioanisole, dibenzothiophene (DBT), and fenthion were selected to investigate the degradation pathway initiated by *CO3-; electron-rich sulfur compounds are particularly reactive towards the *CO3-. Using HPLC, GC, GC-MS and LC-MS for structural confirmation, the major photodegradation products of thioanisole and DBT were the corresponding sulfoxides. The sulfoxide products were further oxidized through reaction with *CO3- to the corresponding sulfone derivatives. Fenthion showed a similar pathway with appearance of fenthion sulfoxide as the major product. The proposed mechanism involves abstraction of an electron on sulfur to form a radical cation, which is then oxidized by dissolved oxygen. Each of the sulfur probes were further investigated in a sunlight simulator under varying matrix conditions. The highest rate constants occurred in the *CO3- matrix, and the lowest occurred in a matrix of dissolved organic carbon (DOC) and bicarbonate. In synthetic and natural field water, thioanisole photodegraded faster than under direct photolysis, with half-lives of 75.1 and 85.8 min, respectively. Fenthion photodegraded more rapidly than thioanisole. DBT photodegraded rapidly in a *CO3- matrix with a half-life of 24.8 min, while the half-life of direct photolysis was 350 min. Photodegradation products of each compound were also investigated. Ultimately, *CO3- was found to contribute toward the photodegradation of sulfur-containing compounds in natural waters.

Elucidation of fipronil photodegradation pathways.

The phenylpyrazole insecticide fipronil (I) photolyzes to its desthio product (II) in aqueous solution. However, the necessity of an intervening oxidation to a sulfone intermediate (III) has not been resolved, and the photodegradation products of II have not been identified. Using GC-MS, HPLC-UV/vis, electrospray MS, (19)F NMR, and GC-TSD, our objective was to characterize the photodegradation pathways of I, which would clarify the role of III, identify products of II, and explain unbalanced mass accounts in previous studies. Findings showed that II is formed directly and photochemically from I, confirmed by the greater stability of III (t(1/2) 112 h), and that successive oxidations of I to III and then a sulfonate (IV) comprise a second pathway. Compound II underwent photodechlorination, substitution of chlorine by trifluoromethyl, and pyrazole ring cleavage. This work is significant to understanding the photochemistry of novel phenylpyrazole pesticides in the environment.

Hydrolysis kinetics of fenthion and its metabolites in buffered aqueous media.

This study investigates the hydrolysis kinetics of fenthion and its five oxidation metabolites in pH 7 and pH 9 buffered aqueous media at 25, 50, and 65 degrees C. Five metabolites and three hydrolysis products were synthesized and purified. The reactant and the corresponding hydrolysis products were determined by HPLC. Rate constant and half-life studies revealed that fenthion and its metabolites were relatively stable in neutral media, and their stability decreased as pH increased. The half-lives at 25 degrees C ranged from 59.0 days for fenthion to 16.5 days for fenoxon sulfone at pH 7, and from 55.5 days for fenthion to 9.50 days for fenoxon sulfone at pH 9; half-lives were greatly reduced at elevated temperatures. The activation energy (E(a)) was found to range from 16.7 to 22.1 kcal/mol for the compounds investigated. The phenol hydrolysis product of fenthion and fenoxon, 3-methyl-4-methylthiophenol was not stable in pH 7 and pH 9 buffered solutions at 50 degrees C, whereas 3-methyl-4-methylsulfonylphenol and 3-methyl-4-methylsulfinylphenol were relatively stable under the same conditions. At pH 9, the primary hydrolysis mechanisms of fenthion and its oxidation metabolites were combination of hydroxide ion and neutral water molecule attacking on the P atom to form corresponding phenol derivatives. Under neutral conditions, the primary hydrolysis mechanisms of fenthion and its oxidation metabolites were assumed to be the combination of water molecule attacking on the P atom to form phenol derivatives and on the C atom to yield dealkylation products.

Photodegradation of metolachlor: isolation, identification, and quantification of monochloroacetic acid.

The photolysis of metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] in a sunlight simulator under actinic radiation was investigated. The focus of the study was to determine the extent of monochloroacetic acid (MCA) production. MCA was concentrated and derivatized from photolysate as the n-propyl ester using propanol and sulfuric acid and then identified as the ester using GC/MS and GC/ECD. On the basis of regression analysis, it was shown that the direct photodegradation of approximately 10 microM metolachlor followed pseudo-first-order kinetics with respect to the metolachlor concentration, and the half-life of the herbicide ( approximately 74 h) was independent of the pH of the medium. Photolysis in synthetic field water (SFW) resulted in a significant reduction of photolysis time (t(1/2) approximately 9 h). Direct photolysis experiments indicate a 5.19 +/- 0.81% (n=3) conversion of metolachlor to MCA, while photolysis in synthetic field water and in a Don River water sample resulted in 29.8 +/- 4.6% (n = 3) and 12.6 +/- 4.1% (n = 3) conversion, respectively; MCA was shown to be hydrolytically stable over the time course of the photoreaction. The photodegradation of alachlor, butachlor and a model chloroacetanilide, 2-chloro-N-methylacetanilide, in SFW were also investigated.

Development of an 19F NMR method for the analysis of fluorinated acids in environmental water samples.

This investigation was carried out to evaluate 19F NMR as an analytical tool for the measurement of trifluoroacetic acid (TFA) and other fluorinated acids in the aquatic environment. A method based upon strong anionic exchange (SAX) chromatography was also optimized for the concentration of the fluoro acids prior to NMR analysis. Extraction of the analyte from the SAX column was carried out directly in the NMR solvent in the presence of the strong organic base, DBU. The method allowed the analysis of the acid without any prior cleanup steps being involved. Optimal NMR sensitivity based upon T1 relaxation times was investigated for seven fluorinated compounds in four different NMR solvents. The use of the relaxation agent chromium acetylacetonate, Cr(acac)3, within these solvent systems was also evaluated. Results show that the optimal NMR solvent differs for each fluorinated analyte. Cr(acac)3 was shown to have pronounced effects on the limits of detection of the analyte. Generally, the optimal sensitivity condition appears to be methanol-d4/2M DBU in the presence of 4 mg/mL of Cr-(acac)3. The method was validated through spike and recovery for five fluoro acids from environmentally relevant waters. Results are presented for the analysis of TFA in Toronto rainwater, which ranged from < 16 to 850 ng/L. The NMR results were confirmed by GC-MS selected-ion monitoring of the fluoroanalide derivative.

Copper (II) complexation in northern California rice field waters: an investigation using differential pulse anodic and cathodic stripping voltammetry.

Differential pulse anodic stripping voltammetry (DPASV) and competitive ligand equilibration-cathodic stripping voltammetry (CLE-CSV) demonstrated that > or = 99% of the dissolved copper in five rice field waters, one river water and a catchment basin water collected at sites in northern California is complexed by natural organic matter. Concentrations of natural copper complexing ligands (CL) ranged from 81 to 426 nM determined by CLE-CSV using the competitive ligand 8-hydroxyquinoline and from 156 to 1374 nM using DPASV. Experimental values for conditional stability constants (with respect to free Cu2+) of natural copper-organic ligand complexes (log K'CuL) fell in the range 10.2-11.2 using DPASV and 11.1-11.5 using CLE-CSV. DPASV analyses revealed evidence of organic matter adsorption to the electrode surface at low dissolved organic carbon (DOC) concentrations (i.e. 200 micrograms l-1 DOC for a 10-min deposition period), for some but not all water samples. Examination of lyophilized, filtered rice field water using scanning electron microscopy (SEM) and pyrolysis gas chromatography mass spectrometry (pyr-GC/MS) did not reveal differences that could be associated with surface active material. Uncomplexed copper accounts for only minor amounts of total copper in rice field waters and natural ligands are expected to influence its effectiveness as an agrochemical.