Assessment of priority phenolic compounds in sediments from an extremely polluted coastal wetland (Lake Maryut, Egypt)

Although high concentrations of trace organic pollutants were recorded along the Egyptian Mediterranean Coast and its corresponding coastal wetlands, no published data are available for the levels of phenolic compounds. Thus, this work aimed to investigate the levels of phenolic compounds in sediments of a heavily polluted coastal wetland (Lake Maryut, Egypt). For that purpose, a method was optimized for the extraction and detection of chlorophenols, methylphenols, and nitrophenols in sediments using GC-MS. Sediments were extracted with 0.1 M NaOH/methanol by sonication. Cleanup of sediment extracts using liquid–liquid extraction and SPE was found important to remove most of the interfering co-extracts. The proposed analytical methodology was validated by analysis of matrix spikes. Detection limits were 0.063–0.694 μg/kg dw for sediments. Good recoveries (70–110%) and precision values (RSD?<?20%) were obtained from the fortification experiments at the parts per billion level in sediments. The method was applied to investigate the level of contamination with phenols in 19 sediment samples from Lake Maryut. Results revealed that higher concentrations were observed in the main basin (MB) of Lake Maryut affected by the discharge of effluents from a primary wastewater treatment plant, direct discharge of industrial effluents, domestic wastes, and agricultural effluents from Qalaa Drain (QD). Chlorophenols (CPs) were the major group detected in the lake sediments followed by methylphenols (MPs) and nitrophenols (NPs). CPs were dominated by 2-, 4-, and 3-chlorophenols. Concentrations of CPs were higher at the north and northwestern parts of the MB indicating the influence of industrial effluents discharged into the lake. On the other hand, higher concentrations of NPs were observed at the south and southwestern parts of the MB, which is subjected to the discharge of agricultural and domestic effluents via QD. Results of the risk assessment revealed that phenol, cresols, 2,4-dinitrophenol, 4-NP, 2-CP, 2,3,4,6-tetrachlorophenol and 2,4-dimethylphenol are contaminants of concern and that adverse ecological effects could possibly occur to benthic species from the exposure to these pollutants in Lake Maryut and thus phenols should be included in monitoring and pollution prevention programs in the Egyptian aquatic environment affected by anthropogenic activities.     

Ionic liquid-based dispersive liquid–liquid microextraction for the determination of formaldehyde in wastewaters and detergents

Spectrophotometry in combination with ionic liquid-based dispersive liquid–liquid microextraction (DLLME) was applied for the extraction and determination of formaldehyde in real samples. The method is based on the reaction of formaldehyde with methyl acetoacetate in the presence of ammonia. The variation in the absorbance of the reaction product was measured at 375?nm. An appropriate mixture of ethanol (disperser solvent) and ionic liquid, 1-hexyl-3-methylimidazoliumhexafluoro-phosphate [C₆MIM][PF₆] (extraction solvent) was rapidly injected into a water sample containing formaldehyde. After extraction, sedimented phase was analyzed by spectrophotometry. Under the optimum conditions, the calibration graph was linear in the range of 0.1–20?ng?mL^?1 with the detection limit of 0.02?ng?mL^?1 and limit of quantification of 0.08?ng?mL^?1 for formaldehyde. The relative standard deviation (RSD%, n?=?5) for the extraction and determination of 0.8?ng?mL^?1 of formaldehyde in the aqueous samples was 2.5%. The results showed that DLLME is a very simple, rapid, sensitive, and efficient analytical method for the determination of trace amounts of formaldehyde in wastewaters and detergents, and suitable results were obtained.     

Simultaneous determination of malachite green, enrofloxacin and ciprofloxacin in fish farming water and fish feed by liquid chromatography with solid-phase extraction

An effective and sensitive method for simultaneous analysis of malachite green (MG), enrofloxacin (ENFLX) and ciprofloxacin (CPFLX) by liquid chromatography-diode array detection with solid-phase extraction (SPE) is developed. The conditions of SPE and LC were investigated and optimised. The effective separation of these compounds was achieved using a ZY1104 C18 column (250 × 4.6 mm, 5 μm) with 20 mM tetrabutyl ammonium bromide (pH 3.0)-acetonitrile as mobile phase and gradient elution. The diode array detection was used at 278 nm for ENFLX and CPFLX and at 613 nm for MG. Under the optimal conditions, the method LOD values of MG, ENFLX and CPFLX were 0.01, 0.07 and 0.10 μg L(?-1) for fish farming water samples and 1.5, 10.5 and 15 μg kg(?-1) for fish feed samples, respectively. The relative recoveries of the three analytes were achieved to be 76.7-82.3% with the RSDs (n = 5) of 3.2-4.6% for spiked fish farming water samples and 78.8-93.7% with the RSDs (n = 5) of 3.1-4.8% for spiked fish feed samples.     

Respirometric Evaluation by Graphical Analysis for Microbial Systems

Analysis of respirometric graphs for system diagnosis has recently drawn much attention due to the nature of the test being a fast method with reliable oxygen uptake (Ou) data. In this study, a new graphical analysis procedure is proposed, using the oxygen uptake rate (OUR) vs. Ou respirogram because of its distinct characteristics that provides easy visual inspection. The OUR plot is typically divided into two respiration phases, and each one of these phases can be simulated by a previously derived analytical equation. Based on the 2-phase model, five characteristic parameters (CPs) were derived for the OUR respirogram. Mathematically the 5 CPs can be related to the system parameters (SPs), including the four Monod kinetic parameters and two operating conditions (initial substrate and biomass concentration). Sensitivity analyses were then conducted to assess the 5 CPs for the level of effect caused by system parameters (SPs). This study also conducted respirometric tests under batch operation to evaluate the applicability of the graphical analysis method. Based on the 5 CPs estimated from the OUR respirogram of the tests, it can be concluded that respirometric tests normally experience the problems associated with initial lag, non-uniform seeding, and inadequate mixing.     

Solid-phase extraction followed by liquid chromatography-time-of-flight-mass spectrometry to evaluate pharmaceuticals in effluents. A pilot monitoring study

The present work provides a multi-residue analytical method for determining a selection of 20 pharmaceuticals from diverse therapeutical classes in hospital effluent wastewater. The method is based on the simultaneous extraction of the target compounds by solid phase extraction (SPE), followed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) analysis. Using TOF-MS, accurate mass measurements within 2 ppm error were obtained for most of the pharmaceuticals studied. Empirical formula information can be obtained by this method, allowing the unequivocal identification of the target compounds in the samples. Validation studies showed that LC-TOF-MS analysis is a valuable new tool for identification and quantification of pharmaceuticals in wastewater. Recoveries, using Oasis HLB cartridges at pH 7, were higher than 75% for all pharmaceuticals, except for ranitidine, 4-methylaminoantipyrine (4-MAA), cefotaxime and omeprazole, which needed specific pH conditions for their extraction. Linearity of response over two orders of magnitude was demonstrated (r > 0.99). Matrix effects resulting in suppression of the response were observed. For most of the compounds ion suppression was less than 39%, except for metronidazole, carbamazepine 10,11-epoxide, naproxen and erythromycin, where the signal suppression was 42%, 59%, 46% and 95%, respectively. A simple and effective approach to minimize or avoid matrix interferences was the 1 : 4 dilution of the SPE extracts. Method detection limits (MDLs) and quantification limits (MQLs) ranged between 4-115 ng l(-1) and 14-384 ng l(-1), respectively. The precision of the method, calculated as relative standard deviation (RSD), ranged from 1.1-19.8% and 1.7-21.7% for intra- and inter-day, respectively. The developed analytical method was applied to the analysis of hospital effluent wastewater during a survey study. 18 of the 20 pharmaceuticals studied were detected at concentration levels of microg l(-1), reaching in some cases concentrations over 100 microg l(-1), and in the case of the analgesic and antipyretic dipyrone metabolite, higher than 1000 microg l(-1).     

Combined toxicity of three chlorophenols 2,4-dichlorophenol, 2,4,6-trichlorophenol and pentachlorophenol to Daphnia magna

The toxicity of single and combined mixtures of 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP) to Daphnia magna was studied. The toxicity ranking of these three single chlorophenols (CPs) to Daphnia magna was PCP > 2,4-DCP > 2,4,6-TCP. The toxic units (TU) approach was used to estimate the combined effects in experiments, the median effective concentration (EC(50)) values were 0.87-1.21 and 0.46-0.59 for binary and ternary mixtures, respectively. Response surface models of General Linear Models (R(2) > 0.90, residual deviation < 3.25) were established for all three binary mixtures. The toxicity for ternary mixtures based on the EC(50)-value and 10% effective concentration (EC(10))-value fixed mixture ratio presented a synergism. The risk based on the single CP's toxicity test may be underestimated. In addition, four approaches (concentration addition, toxicity equivalency factors, effect summation, and independent action) were used for the calculation of combined effects of the mixture. The experimental results showed that concentration addition and toxicity equivalency factor approaches were effective methods for calculation of additive effects of mixtures from binary systems of CPs; while independent action and effect summation (low simulated tail) predicted lower toxicity than experimental results. Limitations of the traditional focus on the effects of single agents were highlighted; hazard assessments ignoring the possibility of joint action of CPs will almost certainly lead to significant underestimations of risk.     

2-Nitroso-1-naphthol as a selective reagent for preconcentration of cobalt by vortex assisted combined with solidification of organic droplet and its determination by flame atomic absorption spectrometry

Highly rapid and selective vortex-assisted liquid–liquid microextraction based on solidification of organic drop has been used for determination of cobalt ion. 2-Nitroso-1-naphthol (2N1N) was used as a selective complexing agent to form stable cobalt–2N1N complex which can be extracted with 1-undecanol at a short time by the assistance of vortex agitator system followed by its determination using flame atomic absorption spectrometry. In vortex assisted, vigorous vortex stream as well as the vibrant effect of vortex system cause very fine droplets of extraction solvent to be produced and extraction occurred at a short time. Some parameters influencing the extraction process such as pH of samples, concentration of 2-nitroso-1-naphthol, extraction solvent volume, extraction time, ionic strength and surfactant addition, as well as interferences were evaluated in detail and optimum conditions were selected. At the optimum conditions, the calibration curve was linear in the range of 15 to 400 μg L^?1 of cobalt ions. The relative standard deviation based on ten replicate analysis of sample solution containing 50 μg L^?1 of cobalt was 3.4 %. The detection limit (calculated as the concentration equivalent to three times of the standard deviation of the blank divided by the slope of the calibration curve after preconcentration) was 5.4 μg L^?1. The accuracy of the proposed method was successfully evaluated by the analysis of certified reference materials. This selective and highly rapid method was used for determination of cobalt ions in different water samples.     

高效液相色谱-串联质谱法同时测定地表水中33种药物

采用固相萃取-高效液相色谱-串联质谱法(SPE-HPLC-MS/MS)建立了地表水中25种抗生素类药物和8种非抗生素类药物的分析方法。通过重点优化质谱参数、色谱条件、样品pH、洗脱溶剂组成及用量等确定了最佳分析条件。水样经过滤、固相萃取柱富集净化后,选择Shim-pack XR-ODS为色谱柱,以乙腈和0.2%甲酸-2 mmol/L乙酸铵-水溶液为流动相进行梯度洗脱,采用电喷雾电离源,在多反应监测模式下(MRM)分析测定,内标法定量。33种药物的仪器定量限为0.012～4.68 ng/L,方法检出限为0.011～7.60 ng/L,地表水加标回收率为53.7%～122%,相对标准偏差为1.22%～32.1%(n=6)。方法成功应用于北京市凉水河12个地表水样分析,共检出32种药物,检出质量浓度为未检出～239 ng/L。利托那韦(RTV)作为新型冠状病毒诊疗方案中推荐的药物在凉水河检出率为100%。     

Preconcentration and determination of lead and cadmium levels in blood samples of adolescent workers consuming smokeless tobacco products in Pakistan

The present study was aimed to evaluate the cadmium (Cd) and lead (Pb) levels in the blood samples of adolescent boys, chewing different smokeless tobacco (SLT) products in Pakistan. For comparative purpose, boys of the same age group (12–15 years), not consumed any SLT products were selected as referents. To determine trace levels of Cd and Pb in blood samples, a preconcentration method, vortex-assisted liquid–liquid microextraction (VLLME) has been developed, prior to analysis by flame atomic absorption spectrometry. The hydrophobic chelates of Cd and Pb with ammonium pyrrolidinedithiocarbamate were extracted into the fine droplets of ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate, while nonionic surfactant, Triton X-114 was used as a dispersing medium. The main factors affecting the recoveries of Cd and Pb, such as concentration of APDC, centrifugation time, volume of IL and TX-114, were investigated in detail. It was also observed that adolescent boys who consumed different SLT products have 2- to 3-fold higher levels of Cd and Pb in their blood samples as compared to referent boys (p?<?0.001).     

Simplification and validation of a large volume polyurethane foam sampler for the analysis of persistent hydrophobic compounds in drinking water

The use of a large volume polyurethane foam (PUF) sampler was validated for rapid extraction of persistent organic pollutants (POPs), such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), in raw water and treated water from drinking water plants. To validate the recovery of target compounds in the sampling process, a (37)Cl-labeled standard was spiked into the 1st PUF plug prior to filtration. An accelerated solvent extraction method, as a pressurized liquid extractor (PLE), was optimized to extract the PUF plug. For sample preparation, tandem column chromatography (TCC) clean-up was used for rapid analysis. The recoveries of labeled compounds in the analytical method were 80-110% (n = 9). The optimized PUF-PLE-TCC method was applied in the analysis of raw water and treated potable water from seven drinking water plants in South Korea. The sample volume used was between 18 and 102 L for raw water at a flow rate of 0.4-2 L min(-1), 95 and 107 L for treated water at a flow rate of 1.5-2.2 L min(-1). Limit of quantitation (LOQ) was a function of sample volume and it decreased with increasing sample volume. The LOQ of PCDD/Fs in raw waters analyzed by this method was 3-11 times lower than that described using large-size disk-type solid phase extraction (SPE) method. The LOQ of PCDD/F congeners in raw water and treated water were 0.022-3.9 ng L(-1) and 0.018-0.74 ng L(-1), respectively. Octachlorinated dibenzo-p-dioxin (OCDD) was found in some raw water samples, while their concentrations were well below the tentative criterion set by the Japanese Environmental Ministry for drinking water. OCDD was below the LOQ in the treated drinking water.     

支撑离子液体膜微萃取-气相色谱法测定水中有机氯农药

摘要：将l-丁基-3-甲基咪唑六氟磷酸离子液体固定于无纺布上形成支撑离子液体膜,结合液相微翠取技术对水样中的有机氯农药进行分离与富集,并用气相色谱法测定。通过试验对影响萃取效率的有关条件进行优化,使该方法在0．500μg／L～10．0μg／L范围内线性良好。方法检出限为0．02μg／L～0．08μg／L,测定0．04μg／L的混合标准溶液平均回收率为75．0％～87．3％,RSD〈7％。     

Emission characteristics of VOCs from three fixed-roof p-xylene liquid storage tanks

This study evaluates emission characteristics of volatile organic compounds (VOCs) caused by standing loss (L _S) and working loss (L _W) of three vertical fixed-roof p-xylene (p-X) liquid tanks during 1-year storage and filling operation. The annual net throughput of the tanks reached 70,446 t, resulting in 9,425 kg of p-X vapor emission including 5,046 kg of L _S (53.54 %) and 4,379 kg of L _W (46.46 %). The estimated L _W of AP-42 displayed better agreement with the measured values of a VOC detector than the estimated L _S of AP-42. The L _S was best correlated with the liquid height of the tanks, while the L _W was best correlated with the net throughput of the tanks. As a result, decreasing vapor space volume of the tanks and avoiding high net throughput of the tanks in a high ambient temperature period were considered as effective means to lessen VOC emission from the fixed-roof organic liquid storage tank.     

超声辅助离子液体-分散液液微萃取-高效液相色谱法测定水中苯胺类化合物

本研究建立了超声辅助离子液体-分散液液微萃取-高效液相色谱测定环境水样中苯胺(AN)、对氟苯胺(4-FA)、对硝基苯胺(4-NA)、对氯苯胺(4-CA)四种苯胺化合物的方法。以最常用的烷基咪唑六氟磷酸盐类离子液体为萃取剂,通过超声加速萃取剂的分散程度,提高了萃取效率。该方法的检测限达到0.1~73 ng/ml,对黄河水和自来水中的加标回收率均在90.5%~113%之间,回收效果良好。与传统的液液萃取相比,该萃取方法具有绿色、快速、富集效果好、有机溶剂消耗小的优点,可以满足环境水体中苯胺类化合物的测定。     

Quantification of triazine herbicides in soil by microwave-assisted extraction and high-performance liquid chromatography

A method for the determination of herbicides residues, triazine (atrazine, metribuzin, ametryn, and terbutryn), in soil samples with high-performance liquid chromatography (HPLC)?CUV detection is described. The proposed method is based on microwave-assisted extraction (MAE) of soil samples for 4 min at 80% of 850-W magnetron outputs in the presence of mixture of solvents (methanol/acetonitrile/ethylacetate). Related important factors influencing the MAE efficiency, such as the solvent type and volume, irradiation energy, and time, were optimized in detail. Calibration curve ranges established using HPLC for metribuzin, atrazine, ametryn, and terbutryn are 1.0?C19.0, 0.9?C18.0, 0.6?C11.0, and 0.7?C11.0 µg mL^???1, respectively. The limits of detection of metribuzin, atrazine, ametryn, and terbutryn are 0.30, 0.24, 0.16, and 0.20 µg mL^???1 while limits of quantification are 1.0, 0.80, 0.50, and 0.60 µg mL^???1, respectively. A Plackett?CBurman factorial design was used as a screening method in order to select the variables that influence MAE extraction. The recoveries of the method at three different spiked levels were assessed by analyzing real soil samples and were found to be in the range of 83.33 ± 0.12?C96.33 ± 0.23 with good precision (<8%).     

Freshwater leeches (Hirudinea) as a screening tool for detecting organic contaminants in the environment

In earlier work, we found that leeches from an industrially polluted creek bioaccumulated chlorophenols to much higher concentrations than other resident benthic invertebrates and fish. We suggested that leeches may have significant potential as biomonitors for these and other organic contaminants in the environment. In this study, we compared the bioaccumulation and depuration of 16 organic compounds, including eight chlorophenols (CPs), lindane, DDT and four derivatives, benzothiazole (BT) and 2-(Methylthio)benzothiazole (MMBT) for three species of leeches. Dina dubia had the highest bioaccumulation capacity for most contaminants, but residues persisted longest in Erpobdella punctata. Helobdella stagnalis appeared capable of degrading some compounds. Half lives of CPs, DDT and DDT derivatives were generally longer than one month. In contrast, half lives were only 1 day for lindane, 1–2.5 days for MMBT and 7 days for BT despite very high initial tissue concentrations of the latter two compounds. Bioconcentration factors for contaminants in leeches were higher than those reported for other aquatic organisms. Half lives for lindane, DDT and DDT derivatives were consistent with the literature for other organisms, but half lives for CPs were much longer. The results suggest that leeches would be excellent biomonitors of both continuous and intermittent contamination of a waterway with CPs and DDT, as they retain these compounds for long periods after exposure. Their usefulness as a screening tool for lindane and benzothiazoles would be limited to chronically contaminated environments.     

Characterization and diurnal variation of size-resolved inorganic water-soluble ions at a rural background site

Water-soluble inorganic ions in aerosol samples have been studied. The sample collection took place during summer in 2003 at a European background site which is operating within the framework of the European Monitoring and Evaluation Program. Gent type PM10 stacked filter unit (SFU) samplers were operated in parallel on a day and night basis to collect particles in separate coarse (2.0-10 microm) and fine (<2.0 microm) size fractions. Particulate masses were measured gravimetrically; the filters from one of the SFU samplers were analyzed by particle-induced X-ray emission spectrometry (PIXE) and instrumental neutron activation analysis (INAA). Filters from the other SFU sampler were analyzed by ion chromatography (IC) for major inorganic anions (MSA-, NO2(-), NO3(-), Cl-, Br-, SO4(2-), oxalate) and cations (Na+, K+, NH4(+), Mg2+, Ca2+). The water-soluble inorganic ions measured were responsible for 44% and 16% of the total fine and coarse particulate mass, respectively. In the fine size fraction, the main ionic components were SO4(2-) and NH4(+) accounting for about 90% of fine ionic mass. In the coarse fraction the main ionic components were Ca2+ and NO3(-), followed by SO4(2-). Significant day and night difference in the mass concentrations was observed only for fine NO3(-). The molar ratios of fine NH4(+) to SO4(2-) indicated their complete neutralization to (NH4)2SO4. According to the cation-to-anion ratios the coarse particles were alkaline, while the fine particles were slightly acidic or neutral. By comparing the corresponding concentrations obtained from PIXE/INAA and IC, we determined the water-extractable part of the individual species. We also investigated the effect of long-range transported air masses on the local air concentrations, and we found that the air quality of this background monitoring station was affected by regional pollution sources.     

Stabilities of 58 volatile organic compounds in fused-silica-lined and SUMMA polished canisters under various humidified conditions

Fused-silica-lined (FSL) canisters and SUMMA polished (SUMMA) canisters were compared for the recoveries and the stabilities of 58 volatile organic compounds (VOCs) at low ppbv (volume/volume) levels under various humidified conditions using a three-stage preconcentration method followed by GC-MS analysis. The target VOCs included non-polar VOCs (e.g. halogenated hydrocarbons and aromatic hydrocarbons) and polar VOCs (e.g. alcohols, ketones, esters, ethers, nitriles and thiols). The three-stage preconcentration method was initially optimized for simultaneous analysis of non-polar and polar VOCs because determination of canister stability is dependent on the accuracy of analytical measurements. The method showed good linearity over the concentration range from 1 to 25 ppbv for all target analytes, and the correlation coefficients were higher than 0.9974. The method detection limits ranged from 0.023 to 0.39 ppbv. The test mixtures loaded in both type of canisters (n = 3) had concentrations of 1.7-2.5 ppbv per compound at ambient pressure under various humidified conditions (%RH = 1.6, 8.0, 27, 39, 53 and >99% with excess water present). All canister samples were initially analyzed on day 0 (after 6-12 h). The effect of competitive adsorption of water vapor and polar VOCs on active sites of interior surface was remarkably observed for SUMMA canisters. Polar VOCs had a greater requirement for water vapor to be present. The RH percentages that ensured good recovery on day 0 were RH > 8% for non-polar VOCs and RH > 27% for polar VOCs (except alcohols under the condition of RH > 99%). All thiols were not recovered from SUMMA canisters under all conditions. FSL canisters showed good recoveries of more than 86% for all VOCs under all conditions on day 0 (except alcohols under the condition of RH > 99%). The recoveries of alcohols in both canisters under the condition of RH > 99% displayed relatively low recoveries in the range 25-76% because of the partitioning effect into condensed water. The canister samples under the conditions of RH 8.0, 27, 53 and > 99% were analyzed for the stability test on days 3, 7, 14 and 28 after loading. All non-polar VOCs were reasonably stable in the FSL canisters under all examined conditions over 28 days. However, several polar VOCs that have relatively lower vapor pressure, e.g. MIBK, butyl acetate and alcohols except ethanol, showed unstable characteristics under relatively dry conditions (RH 8 and 27%) during 28 days. RH > 53% was needed to ensure good stabilities of all analytes except thiols with the recoveries of > 80% over 28 days for both canisters. Although the FSL canister showed good recoveries of more than 86% for thiols on day 0, drastic degradations were observed after day 3 and they were not detected after day 14.     

Biofilm thickness measurement using an ultrasound method in a liquid phase

In this report, the development of an online, noninvasive, measurement method of the biofilm thickness in a liquid phase is presented. The method is based in the analysis of the ultrasound wave pulse-echo behavior in a liquid phase reproducing the real reactor conditions. It does not imply the removal of the biomass from the support or any kind of intervention in the support (pipes) to detect and perform the measurements (non-invasiveness). The developed method allows for its sensor to be easily and quickly mounted and unmounted in any location along a pipe or reactor wall. Finally, this method is an important innovation because it allows the thickness measurement of a biofilm, in liquid phase conditions that can be used in monitoring programs, to help in scheduling cleaning actions to remove the unwanted biofilm, in several application areas, namely in potable water supply pipes.     

Flow injection analysis of trace chromium (VI) in drinking water with a liquid waveguide capillary cell and spectrophotometric detection

Hexavalent chromium (Cr(VI)) is an acknowledged hazardous material in drinking waters. As such, effective monitoring and assessment of the risks posed by Cr(VI) are important analytical objectives for both human health and environmental science. However, because of the lack of highly sensitive, rapid, and simple procedures, a relatively limited number of studies have been carried out in this field. Here we report a simple and sensitive analytical procedure of flow injection analysis (FIA) for sub-nanomolar Cr(VI) in drinking water samples with a liquid core waveguide capillary cell (LWCC). The procedure is based on a highly selective reaction between 1, 5-diphenylcarbazide and Cr(VI) under acidic conditions. The optimized experimental parameters included reagent concentrations, injection volume, length of mixing coil, and flow rate. Measurements at 540 nm, and a 650-nm reference wavelength, produced a 0.12-nM detection limit. Relative standard deviations for 1, 2, and 10 nM samples were 5.6, 3.6, and 0.72 % (n?=?9), and the analysis time was <2 min sample^?1. The effects of salinity and interfering ions, especially Fe(III), were evaluated. Using the FIA-LWCC method, different sources of bottled waters and tap waters were examined. The Cr(VI) concentrations of the bottled waters ranged from the detection limit to ～20 nM, and tap waters collected from the same community supply had Cr(VI) concentration around 14 nM.     

Analysis of per- and polyfluorinated alkyl substances in air samples from Northwest Europe

Air samples were collected from 4 field sites in Europe: 2 sites from the UK, Hazelrigg (semi-rural) and Manchester (urban); 1 site from Ireland: Mace Head (rural); and 1 site from Norway: Kjeller (rural). Additionally, air samples were taken from indoor locations in Troms?, Norway. Air samples were collected using high-volume air samplers employing sampling modules containing glass-fibre filters (GFFs, particle phase), and glass columns with a polyurethane foam (PUF)-XAD-2-PUF sandwich (gaseous phase). Typical outdoor air volumes required for the determination of per- and polyfluorinated alkyl substances (PFAS) ranged from 500-1800 m3. GFFs and PUF-XAD columns were analysed separately to obtain information on phase partitioning. All air samples were analysed for volatile, neutral PFAS, with selected GFF samples halved for analysis of both neutral and airborne particle-bound ionic PFAS. Volatile PFAS were extracted from air samples by cold-column immersion with ethyl acetate, and were analysed by gas chromatography-mass spectrometry in the positive chemical ionisation mode (GC-PCI-MS). Ionic PFAS were extracted from GFFs by sonication in methanol, and were analysed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) using electrospray ionisation in the negative ion mode (ESI-). Perfluorooctanoate (PFOA) was often the predominant analyte found in the particulate phase at concentrations ranging from 1-818 pg m(-3), and 8:2 fluorotelomer alcohol (FTOH) and 6:2 FTOH were the prevailing analytes found in the gas phase, at 5-243 pg m(-3) and 5-189 pg m(-3), respectively. These three PFAS were ubiquitous in air samples. Many other PFAS, both neutral and ionic, were also present, and levels of individual analytes were in the 1-125 pg m(-3) range. Levels of some PFAS exceeded those of traditional persistent organic pollutants (POPs). In this study, the presence of 12:2 FTOH and fluorotelomer olefins (FTolefins), and ionic PFAS other than perfluorooctane sulfonate (PFOS) and PFOA, are reported in air samples for the first time. Concentrations of neutral PFAS were several orders of magnitude higher in indoor air than outdoor air, making homes a likely important diffuse source of PFAS to the atmosphere. Our repeated findings of non-volatile ionic PFAS in air samples raises the possibility that they might directly undergo significant atmospheric transport on particles away from source regions, and more atmospheric measurements of ionic PFAS are strongly recommended.