Measurements of non-methane hydrocarbons, DOC in surface ocean waters and aerosols over the Nordic seas during polarstern cruise ARK-XX/1 (2004)

To explore processes leading to the formation of volatile organic compounds at the sea surface and their transfer to the atmosphere, whole air, marine aerosols, and surface ocean water DOC were simultaneously sampled during June-July 2004 on the Nordic seas. 19 C(2)-C(6) non-methane hydrocarbons (NMHCs) in the air samples are reported from nine sites, spanning a range of latitudes. Site-to-site variability in NMHC concentrations was high, which suggests variable, local sources for these compounds studied. Total DOC in surface waters sampled ranged from 0.84 mg l(-1) (Fram Strait) to 1.06 mg l(-1) (East Greenland Current), and decreased 6-8% with 24h UV-A irradiation. Pentanes and hexanes, as well as acetone and dimethylsulfide, were identified in the seawater samples using solid-phase microextraction/GC-MS. All these compounds are volatile enough that exchange with the atmosphere can be expected, and the detection of the hydrocarbons in particular is consistent with a marine source for these in the air samples. Size-fractionated aerosols from the same sampling regions were analysed by SEM-EDX and contained sea salt, marine sulfates, and carbonates. A culturable bacterium was isolated from the large (9.9-18 microm) fraction at one site, and identified by 16S rRNA PCR analysis as Micrococcus luteus, raising the possibility that marine bioaerosols could transfer marine organic carbon to the aerosol phase and thus influence formation of VOCs above the remote oceans.     

Occurrence and source characterization of perfluorochemicals in an urban watershed

Perfluorochemicals (PFCs) are used in numerous applications, mainly as surfactants, and occur ubiquitously in the environment as complex mixtures. This study was undertaken to characterize the occurrence and sources of commonly detected PFC compounds in surface waters of the Marina catchment, a watershed that drains an urbanized section of Singapore. Of the 19 target PFCs, 13 were detected with perfluorooctanoic acid (PFOA) (5-31 ng L⁻¹) and perfluorooctane sulfonate (PFOS) (1-156 ng L⁻¹) being the dominant components. Other compounds detected included perfluoroalkyl carboxylates (C7-C12) and perfluoroalkyl sulfonates (C6 and C8). Sulfonamide compounds detected 2-(N-ethylperfluorooctanesulfonamido) acetic acid (N-EtFOSAA), 2-(N-methylperfluorooctanesulfonamido) acetic acid (N-MeFOSAA), perfluorooctanesulfonamido acetic acid (FOSAA) and perfluorooctanesulfonamide (FOSA) were putative transformation products of N-EtFOSE and N-MeFOSE, the N-ethylated and N-methylated ethyl alcohol derivatives, respectively. Surface water concentrations were generally higher during dry weather than during storm water flow: the median concentrations of total PFCs in dry and wet weather were 57 and 138 ng L⁻¹ compared to 42 and 79 ng L⁻¹, respectively, at Stamford and Alexandra canal, suggesting the presence of a continuous source(s) which is subject to dilution during storm events. In rain water, median concentrations were 6.4 ng L⁻¹, suggesting rain contributed from 12-25% to the total PFC load for non-point source sites. The longitudinal concentration profile along one of the canals revealed a point source of sulfonated PFCs (PFOS), believed to originate from aqueous film-forming foam (AFFF). Sources were characterized using principal component analysis (PCA) and by plotting PFHxS/PFOA against PFOS/PFOA. Typical surface waters exhibit PFOS/PFOA and PFHxS/PFOA ratios below 0.9 and 0.5, respectively. PCA plots reveal waters impacted by “non-typical” PFC sources in Alexandra canal.     

Pinonaldehyde and some other organics in rain and snow in central Japan.

Solvent-extractable organic compounds in the rain and snow collected at local cities in the mountainous region in central Japan, were analyzed by GC/MS and GC. Pinonaldehyde (2,2-dimethyl-3-acetyl-cyclobutyl-ethanal), an atmospheric reaction product of alpha-pinene, was detected in the rain and snow for the first time, and n-alkanes (C17-C33), fatty acids (C8-C23), and benzoic acid were also detected as major organic components. Concentrations of pinonaldehyde, C17-C33 n-alkanes, C8-C11 fatty acids, C12-C23 fatty acids and benzoic acid ranged between <0.02-13, 0.10-35, 0.55-5.7, 4.2-19 and <0.02-6.0 microg/l, respectively. Their composition showed some difference in summer and winter. In summer, fatty acids and benzoic acid were more abundant, while pinonaldehyde and n-alkanes were much less. Higher photochemical reactivity and higher bioactivity in summer could explain these seasonal changes except for pinonaldehyde, which would suffer from further oxidation in the atmosphere after its photochemical production from alpha-pinene. Predominance of pinonaldehyde and C12-C23 fatty acids in the rain and snow showed a remarkable contrast to n-alkanes in aerosol phase, which were the most abundant components. It indicated that oxygenated products from biogenic compounds might be important as cloud condensation nuclei in forest areas.     

Biogeochemical dynamics of perfluorinated alkyl acids and sulfonates in the River Seine (Paris, France) under contrasting hydrological conditions

The biogeochemical dynamics of 15 perfluorinated compounds (PFCs) were investigated in a heavily urbanised river (River Seine, Paris, France). The target compounds included C4-C10 sulfonates and C5-C14 acids; eleven PFCs were detected and ∑PFCs ranged between 31 and 91 ng L⁻¹ (median: 47 ng L⁻¹). The molecular pattern was dominated by the perfluoroalkyl sulfonates PFHxS and PFOS (>54% of ∑PFCs), which were the only PFCs quantified in both the dissolved and particulate phases. For these PFCs, the sorbed fraction positively correlated with suspended sediment levels. Total PFC levels negatively correlated with river flow rate, which varied between 150 and 640 m³ s⁻¹. This suggests the predominance of point sources (likely WWTP effluent discharge), but a contribution of non-point sources such as combined sewer overflow could not be excluded. The annual PFC mass flow was estimated at 500 kg, which is less than observed for other large European rivers.     

Comparative study on the susceptibility of freshwater species to copper-based pesticides

Copper compounds have been intentionally introduced into water bodies as aquatic plant herbicides, algicides and molluscicides. Copper-based fertilizers and fungicides have been widely used in agriculture as well. Despite the fact that copper is an essential element for all biota, elevated concentrations of this metal have been shown to affect a variety of aquatic organisms. Nonetheless, comparative studies on the susceptibility of different freshwater species to copper compounds have seldom been performed. This study was conducted to compare toxicity of copper-based pesticides (copper oxychloride, cuprous oxide and copper sulfate) to different freshwater target (Raphidocelis subcapitata, a planktonic alga and Biomphalaria glabrata, a snail) and non-target (Daphnia similis, a planktonic crustacean and Danio rerio, a fish) organisms. Test water parameters were as follows: pH = 7.4 +/- 0.1; hardness 44 +/- 1 mg/l as CaCO3; DO 8-9 mg/l at the beginning and > 4 mg/l at the end; temperature, fish and snails 25 +/- 1 degrees C, Daphnia 20 +/- 2 degrees C, algae 24 +/- 1 degrees C. D. similis (immobilization), 48-h EC50s (95% CLs) ranging from 0.013 (0.011-0.016) to 0.043 (0.033-0.057) mg Cu/l, and R. subcapitata (growth inhibition), 96-h IC50s from 0.071 (0.045-0.099) to 0.137 (0.090-0.174) mg Cu/l, were the most susceptible species. B. glabrata (lethality), 48-h LC50s from 0.179 (0.102-0.270) to 0.854 (0.553-1.457) mg Cu/l, and D. rerio (lethality), 48-h LC50s 0.063 (0.045-0.089), 0.192 (0.133-0.272) and 0.714 (0.494-1.016) mg Cu/l, were less susceptible than Daphnia to copper-based pesticides. Findings from the present study therefore suggest that increased levels of copper in water bodies is likely to adversely affect a variety of aquatic species.     

Levels and pattern of volatile organic nitrates and halocarbons in the air at Neumayer Station (70 degrees S), Antarctic

Levels and patterns of C1-C4/C9 organic nitrates were measured for the first time in Antarctica. The sampling was done by adsorptive enrichment on Tenax TA followed by thermodesorption cold-trap high resolution capillary gas chromatography with electron capture detection. 2-70 1 air on-column have been analyzed this way. C1-C9 alkyl mononitrates, C2-C4 alkyl dinitrates, C2-C4 hydroxy alkyl nitrates, and halocarbons could be identified in air samples collected near the German Neumayer Research Station, Antarctica, in February 1999. Volatile biogenic and anthropogenic halocarbons were used to assess the origin of the air parcels analyzed. The average concentration measured for sigmaC2-C6 alkyl nitrates was in the range of 9.2 +/- 1.8 ppt(v), while the sum of the mixing ratios of six C2-C4 hydroxy alkyl nitrates was in the range of 1.1 +/- 0.2 ppt(v). Moreover, C2-C4 alkyl dinitrates were found at levels near the detection limit of 0.1-0.5 ppt(v). The concentrations of organic nitrates found in Antarctic air represent ultimate baseline levels due to chemical and physical loss processes during long-range transport in the air. The South Atlantic and the Antarctic Ocean as a general secondary source for organic nitrates in terms of an air/sea exchange equilibrium has to be evaluated yet, but it seems logical. Our results confirm the common assumption that there are no biogenic marine sources of C2-C9 organonitrates. We have found a level of > 80 ppt(v) for methyl nitrate. This level if it can be confirmed in a systematic survey requires a strong biogenic source of methyl nitrate in the Antarctic Ocean.     

Determination of benzene, toluene, ethylbenzene, xylenes in water at sub-ng l-1 levels by solid-phase microextraction coupled to cryo-trap gas chromatography-mass spectrometry

A trace analytical method of benzene, toluene, ethylbenzene and xylenes (BTEX) in water has been developed by using headspace solid-phase microextraction (HS-SPME) coupled to cryo-trap gas chromatography-mass spectrometry (GC-MS). The chromatographic peak shape for BTEX was improved by using cryo-trap equipment. The HS-SPME experimental procedures to extract BTEX from water were optimized with a 75 microm carboxen/polydimethylsiloxane (CAR/PDMS)-coated fiber at a sodium chloride concentration of 267 g l(-1), extraction for 15 min at 25 degrees C and desorption at 290 degrees C for 2 min. Good linearity was verified in a range of 0.0001-50 microg l(-1) for each analyte (r(2)=0.996-0.999). The limits of detection (LODs) of BTEX in water reached at sub-ng l(-1) levels. LODs of benzene, toluene, ethylbenzene, m/p-xylene and o-xylene were 0.04, 0.02, 0.05, 0.01 and 0.02 ng l(-1), respectively. The proposed analytical method was successfully used for the quantification of trace BTEX in ground water. The results indicate that HS-SPME coupled to cryo-trap GC-MS is an effective tool for analysis of BTEX in water samples at the sub-ng l(-1) level.     

Determination and partitioning behavior of perfluoroalkyl carboxylic acids and perfluorooctanesulfonate in water and sediment from Dianchi Lake, China

Perfluorinated compounds (PFCs) have received much attention on their distribution in various matrices including water bodies, precipitations, sediment and biota in different areas globally, however, little attention has been paid to their occurrence and distribution in urban lakes. In this study, water and sediment samples collected from 26 sites in Dianchi Lake, a plateau urban lake in the southwestern part of China were analyzed via high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) for ten analytes involving nine perfluoroalkyl carboxylic acids (PFOAs) and perfluorooctanesulfonate (PFOS). Total levels of PFCs were 30.98 ± 32.19 ng L(-1) in water and 0.95 ± 0.63 ng g(-1) in sediment. In water samples PFOA was the dominant PFC contaminant, with concentrations ranging from 3.41 to 35.44 ng L(-1), while in sediments PFOS was the main PFC contaminant at levels from 0.07-0.83 ng g(-1) dry weight. Field-based sediment water distribution coefficients (K(D)) were calculated and corrected for organic carbon content (K(oc)), which reduced variability among samples. The log K(oc) ranged from 2.54 to 3.57 for C8-C12 perfluorinated carboxylic acids, increasing by 0.1-0.4 log units with each additional CF2 moiety. The log K(oc) of PFOS was 3.35 ± 0.32. Magnitudes and trends in log K(D) or log K(oc) appeared to agree well with previously published laboratory data. Results showed that different PFC composition profiles were observed for samples from the lake water and sediments, indicating the presence of dissimilar characteristics of the PFCs compounds, which is important for PFC fate modeling and risk assessment.     

Color and COD removal from wastewater containing Reactive Black 5 using Fenton's oxidation process

In this study, Reactive Black 5 (RB5) was removed from synthetic wastewater using Fenton's oxidation (FO) process. Experiments were conducted on the samples containing 100 and 200 mg l(-1) of RB5 to remove the dye toxicity. Seventy-five milligram per litre of RB5 caused 25% toxicity on 24-h born daphnids whereas 100 mg l(-1) of RB5 displayed 100% toxicity on Daphnia magna. The study was performed in a systematic approach searching optimum values of FeSO(4) and H(2)O(2) concentrations, pH and temperature. Optimum pH and temperature for 100 mg l(-1) of RB5 were observed as 3.0 and 40 degrees C, respectively, using 100 mg l(-1) of FeSO(4) and 400 mg l(-1) of H(2)O(2) resulted in 71% chemical oxygen demand (COD) and 99% color removal. For 200 mg l(-1) of RB5, 84% COD removal was obtained using 225 mg l(-1) of FeSO(4) and 1000 mg l(-1) of H(2)O(2) yielding 0.05 molar ratio at pH 3.0 and 40 degrees C. Color removal was also more than 99%. The optimum conditions determined in accordance with the literature data. The H(2)O(2) requirement seems to be related to initial COD of the sample. FeSO(4)/H(2)O(2) ratios found were not changed for both concentrations. The temperature affected the COD removal significantly at high degrees. Toxicity was completely removed for each concentration of RB5 at optimum removal conditions.     

Analysis of perfluorooctanoate (PFOA) and other perfluorinated compounds (PFCs) in the River Po watershed in N-Italy

C7-C11 perfluorinated carboxylates (PFACs) and perfluorooctansulfonate (PFOS) were analysed in selected stretches of the River Po and its major tributaries. Analyses were performed by solid-phase extraction (SPE) with Oasis HLB cartridges and methanol elution followed by LC-MS-MS detection using 13C-labelled internal standards. High concentration levels ( approximately 1.3 microg l(-1)) of perfluorooctanoate (PFOA) were detected in the Tánaro River close to the city Alessandria. After this tributary, levels between 60 and 337 ng l(-1) were measured in the Po River on several occasions. The PFOA concentration close to the river mouth in Ferrara was between 60 and 174 ng l(-1). Using the river discharge flow data in m3 s(-1) at this point (average approximately 920 m3 s(-1) for the year 2006), a mass load of approximately 0.3 kg PFOA per hour or approximately 2.6 tons per year discharged in the Adriatic Sea has been calculated. PFOS concentration levels in the Po River at Ferrara were approximately 10 ng l(-1).     

Biogenic volatile organic compound emissions (BVOCs). I. Identifications from three continental sites in the U.S

Vegetation composition and biomass were surveyed for three specific sites in Atlanta, GA; near Rhinelander, WI; and near Hayden, CO. At each research site emissions of biogenic volatile organic compounds (BVOCs) from the dominant vegetation species were sampled by enclosing branches in bag enclosure systems and sampling the equilibrium head space onto multi-stage solid adsorbent cartridges. Analysis was performed using a thermal desorption technique with gas chromatography (GC) separation and mass spectrometry (MS) detection. Identification of BVOCs covering the GC retention index range (stationary phase DB-1) from approximately 400 to 1400 was achieved (volatilities C4-C14).     

Assessment of five bioaccessibility assays for predicting the efficacy of petroleum hydrocarbon biodegradation in aged contaminated soils

In this study, the bioaccessibility of petroleum hydrocarbons in aged contaminated soils (1.6-67gkg(-1)) was assessed using four non-exhaustive extraction techniques (100% 1-butanol, 100% 1-propanol, 50% 1-propanol in water and hydroxypropyl-β-cyclodextrin) and the persulfate oxidation method. Using linear regression analysis, residual hydrocarbon concentrations following bioaccessibility assessment were compared to residual hydrocarbon concentrations following biodegradation in laboratory-scale microcosms in order to determine whether bioaccessibility assays can predict the endpoint of hydrocarbon biodegradation. The relationship between residual hydrocarbon concentrations following microcosm biodegradation and bioaccessibility assessment was linear (r(2)=0.71-0.97) indicating that bioaccessibility assays have the potential to predict the extent of hydrocarbon biodegradation. However, the slope of best fit varied depending on the hydrocarbon fractional range assessed. For the C(10)-C(14) hydrocarbon fraction, the slope of best fit ranged from 0.12 to 0.27 indicating that the non-exhaustive or persulfate oxidation methods removed 3.5-8 times more hydrocarbons than biodegradation. Conversely, for the higher molecular weight hydrocarbon fractions (C(29)-C(36) and C(37)-C(40)), biodegradation removed up to 3.3 times more hydrocarbons compared to bioaccessibility assays with the resulting slope of best fit ranging from 1.0-1.9 to 2.0-3.3 respectively. For mid-range hydrocarbons (C(15)-C(28)), a slope of approximately one was obtained indicating that C(15)-C(28) hydrocarbon removal by these bioaccessibility assays may approximate the extent of biodegradation. While this study demonstrates the potential of predicting biodegradation endpoints using bioaccessibility assays, limitations of the study include a small data set and that all soils were collected from a single site, presumably resulting from a single contamination source. Further evaluation and validation is required using soils from a range of hydrocarbon contamination sources in order to develop robust assays for predicting bioremediation endpoints in the field.     

Perfluoroalkyl compounds in municipal WWTPs in Tianjin, China—concentrations, distribution and mass flow

BACKGROUNDS: Perfluorinated compounds (PFCs) have drawn much attention due to their environmental persistence, ubiquitous existence, and bioaccumulation potential. Wastewater treatment plants (WWTPs) are fundamental utilities in cities, playing an important role in preventing water pollution by lowering pollution load in waste waters. However, some of the emerging organic pollutants, like PFCs cannot be efficiently removed by traditional biological technologies in WWTPs, and some even increase in effluents compared to influents due to the incomplete degradation of precursors. Hence, WWTPs are considered to be a main point source in cities for PFCs that enter the aquatic environment. However, the mass flow of PFCs from WWTPs has seldom been analyzed for a whole city. Hence, in the present study, 11 PFCs including series of perfluoroalkyl carboxylic acids (PFCAs, C4-C12) and two perfluoroalkyl sulfonates (PFASs, C6 and C8) were measured in WWTP influents and effluents and sludge samples from six municipal WWTPs in Tianjin, China. Generation and dissipation of the target PFCs during wastewater treatment process and their mass flow in effluents were discussed. RESULTS: All the target PFCs were detected in the six WWTPs, and the total PFC concentration in different WWTPs was highly influenced by the population density and commercial activities of the corresponding catchments. Perfluorooctanoic acid (PFOA) was the predominant PFC in water phase, with concentrations ranging from 20 to 170 ng/L in influents and from 30 to 145 ng/L in effluents. Concentrations of perfluoroalkyl sulfonates decreased substantially in the effluent compared to the influent, which could be attributed to the sorption onto sludge, whereas concentrations of PFOA and some other PFCAs increased in the effluent in some WWTPs due to their weaker sorption onto solids and the incomplete degradation of precursors. Perfluorooctane sulfonic acid (PFOS) was the predominant PFC in sludge samples followed by PFOA, and their concentrations ranged from 42 to 169 g/kg and from 12 to 68 g/kg, respectively. Sludge-wastewater distribution coefficients (log K(d)) ranged from 0.62 to 3.87 L/kg, increasing with carbon chain length of the homologues. The mass flow of some PFCs in the effluent was calculated, and the total mass flow from all the six municipal WWTPs in Tianjin was 26, 47, and 3.5 kg/year for perfluorohexanoic acid, PFOA, and PFOS, respectively.     

Degradation of phenol and cresols at low temperatures using a suspended-carrier biofilm process

Degradation of phenol and o-, m- and p-cresol at a concentration of 150 mg l(-1) of each compound was studied in a suspended-carrier biofilm process consisting of two aerobic stages. The fungus Mortierella sarnyensis Mil'ko dominated the microflora in the first reactor, while bacteria dominated in the second reactor. The process was studied at 4, 7, 11 and 15 degrees C. The results from the experiments showed the process to be relatively efficient even at 4 degrees C. The degradation rate was 33% of that at 15 degrees C for o-cresol. Both phenol and the cresols were degraded in the first reactor and a new peak appeared in the HPLC-chromatograms indicating the formation of one or more intermediate compounds in the first stage. These compounds were however degraded to below the detection limit in the second reactor. Small new peaks appeared in the chromatograms of the outlet from the second reactor at the maximum loading rates.     

A simple spectrophotometric method for the determination of cobalt in industrial, environmental, biological and soil samples using bis(salicylaldehyde)orthophenylenediamine

Bis(salicylaldehyde)orthophenylenediamine (BSOPD) has been proposed as new analytical reagent for the direct non-extractive spectrophotometric determination of cobalt. It reacts with cobalt in slightly acidic (0.0002-0.001 M H(2)SO(4)) 50% 1,4-dioxanic medium to form a red-orange chelate with a molar ratio 1:1. The reaction is instantaneous and the maximum absorbance was obtained at 458 nm and remains constant for over 24h. The average molar absorption coefficient and Sandell's sensitivity were found to be 1.109 x 10(4)l mol(-1)cm(-1) and 20 ng cm(-2) of Co(II), respectively. Linear calibration graph was obtained for 0.1-15 mg l(-1) of Co(II) with a correlation coefficient value of 0.995 for Co-BSOPD complex. Large excess of 44 cations, anions and complexing agents do not interfere in the determination. The method was successfully used in the determination of cobalt(II) from synthetic mixture and certified reference materials for the purpose of validating the method and the results of analyses were found to be excellent agreement with those of actual values. This developed method was also used for determination of cobalt in some environmental waters (potable and polluted), biological (blood and urine) and soil samples and solution containing both cobalt(II) and cobalt(III). The results of the proposed method for biological samples were comparable with AAS and were found to be in good agreement. The method has high precision and accuracy (s=+/-0.01 for 0.5 mg l(-1)).     

Effect of temperature on the disappearance of four triazine herbicides in environmental waters

The influence of temperature on the disappearance of four s-triazine herbicides, terbuthylazine, simazine, atrazine and prometryn was studied in sea, river and groundwaters spiked with approx. 5 mg l(-1) of each during long-term laboratory incubation. Residues were analyzed by GC-NPD and confirmed by GC-MSD. No clean-up was necessary and a micro on-line method for the determination of herbicide residues was used. The results showed that temperature had little effect on the behaviour of the four herbicides in river and seawaters but strongly affected their behaviour in groundwater. Simazine was the most readily affected compound in sea, river and groundwaters, while terbuthylazine and atrazine were the most persistent in all cases, especially in riverwater. Half-lives ranged from 41 days (constant rate = 0.017 days(-1)) to 196 days (constant rate = 0.003 days(-1)) for simazine (40 degrees C) and terbuthylazine (20 degrees C), respectively, in riverwater. Only for terbuthylazine in riverwater was the remaining percentage at the end of the experiment higher than 50% (58%, 3.21 mg l(-1)). In the other cases, the remaining percentage varied from 4% (0.20 mg l(-1), 40 degrees C) to 43% (2.25 mg l(-1), 20 degrees C) for simazine and terbuthylazine, respectively, in groundwater.     

The environmental photolysis of perfluorooctanesulfonate,perfluorooctanoate, and related fluorochemicals

A field study on the photolysis of perfluoroalkyl substances (PFASs) was conducted at high altitudes in Mt. Mauna Kea (Hawaii, USA; 4200 m) and Mt. Tateyama (Toyama, Japan; 2500 m). Results of photolysis of PFASs in the field were further confirmed in laboratory studies. Perfluorooctanesulfonate (PFOS), which is perceived as a non-degradable chemical in the environment, can undergo photolysis. Long chain PFASs can be successively dealkylated to short chain compounds such as perfluorobutyric acid (PFBA) and perfluorobutane sulfonate (PFBS), but the short chain compounds were relatively more resistant to photodegradation. These results suggest that environmental levels of short chain PFASs would increase both due to their formation from photolysis of long chain PFASs and from direct releases. Earlier studies on photolysis of PFASs were focused on the formation of perfluorocarboxylic acids (PFCAs) and perfluorosulfonic acids (PFSAs) from precursor compounds (such as fluorotelomer alcohols) under laboratory conditions. Our study suggests that PFSAs and PFCAs themselves can undergo photodegradation in the environment.     

Photochemical decomposition of environmentally persistent short-chain perfluorocarboxylic acids in water mediated by iron(II)/(III) redox reactions

The photochemical decomposition of short-chain (C(3)-C(5)) perfluorocarboxylic acids (PFCAs) was investigated. Direct photolysis in water proceeded slowly with the 220- to 460-nm light emission from a xenon-mercury lamp to form F(-), CO(2), and shorter-chain PFCAs. Addition of a small amount of Fe(3+) to the aqueous solutions of the PFCAs dramatically enhanced their photochemical decomposition under an oxygen atmosphere: when the (initial PFCA)/(initial Fe(3+)) molar ratio was 13.5 (initial PFCA concentration=67.3mM), the pseudo-first-order rate constants for the PFCA decomposition were 3.6-5.3 times those with photolysis alone, and the turnover number for the catalytic PFCA decomposition [i.e., (moles of decomposed PFCA)/(moles of initial Fe(3+))] reached 6.71-8.68 after 24h of irradiation. The catalysis can be explained by photoredox reactions between PFCA, Fe(3+)/Fe(2+) and oxygen via photo-induced complexation of Fe(3+) with the PFCAs.     

Magnetic molecularly imprinted polymer prepared by microwave heating for confirmatory determination of chloramphenicol in chicken feed using high-performance liquid chromatography-tandem mass spectrometry

Abstract

A magnetic molecularly imprinted polymer (MMIP) for chloramphenicol was prepared using a surface-imprinted and microwave-heating-induced polymerization method. The surfaces of the magnetic particles were first double-bond functionalized with 3-(trimethoxysilyl)propyl methacrylate (γ-MPS), followed by the copolymerization of 4-vinyl pyridine (4-VP) and trimethylolpropane trimethacrylate (TRIM) in the presence of chloramphenicol as a template and 1,1-azobis(cyclohexane-carbonitrile) (ABCN) as an initiator in a mixture of dimethyl sulfoxide and water with microwave heating at 80°C. The magnetic polymer possesses supraparamagnetic properties and was used to concentrate and cleanup chicken feed extract, followed by chromatographic separation using a Lichrospher®100 RP C8 column and detection with two multi-reaction monitoring transitions at m/z 321→ 152 and m/z 321→ 257. The mean recoveries obtained at two spiking levels were in the range of 94.6–100% The relative intra- and inter-day standard deviations were in the range of 1.4–2.6% and 5.1–5.7%, respectively. The detection limit of the method was 0.12 µg kg^?1. This confirmatory method was successfully applied to determine chloramphenicol in chicken feed samples.     

Distribution and desorption of perfluorinated compounds in fractionated sediments

This study provides particle-scale understanding of perfluorinated compounds (PFCs) distribution in sediments collected from two locations in Tianjin, China. The sediments were fractionated according to particle size and density. Even though lower density carbonaceous fractions contributed only 17.8-22.3% of the total sediment mass, they displayed stronger affinity to PFCs with much higher PFC concentrations than in the heavy fractions. Hydrophobic interaction predominated the partition of longer chain PFCs while electrostatic interaction could affect the sorption of short chain PFCs in sediment fractions. The individual PFC concentrations increased with increasing perfluorocarbon chain length, and the concentrations of perfluoroalkanesulfonates (PFSAs) in the same sediment fraction were higher than perfluorocarboxylates (PFCAs) with the same chain length. Log K(oc) was in the range of 1.70-3.80 for C5-C12 PFCAs and 1.75-2.97 for C4-C8 PFSAs. Desorption experiments indicated desorption became difficult as the chain length increased, and PFSAs were harder to be desorbed than the corresponding PFCAs.