Acetaldehyde residue in polyethylene terephthalate (PET) bottles

A simple sample preparation technique was developed for rapid analysis of acetaldehyde residue in Polyethylene Terephthalate (PET) bottles. A laboratory-built heating system was used and coupled with gas chromatography-flame ionization detector (GC-FID) at optimized conditions. The results were a tremendous reduction of the sample preparation time from 24 hours, for the conventional method, to only one hour. The analysis took only 1.5 min with other good analytical performances i.e. a low detection limit, 0.3 ng mL^{? 1} and a wide linear dynamic range, 0.3 ng mL^{? 1} to 6.6 μ g mL^{? 1} with R² > 0.99.Acetaldehyde residue in freshly blown bottles were analyzed and found in the range of 0.4 to 1.1 ng mL^{? 1}. The results were good agreement with the conventional 24-hour airspace method (P < 0.01). The PET-bottle sampling technique was also developed to minimize the complication of sample transportation and pre-concentration. A purge and trap technique was found to be the most suitable. Then, it was implemented and compared, the results showed no significant difference (P < 0.01) with and without purge and trap.     

Tube-Immunoassay for Rapid Detection of Carbaryl Residues in Agricultural Products

An antibody-based rapid, quantitative, and qualitative tube enzyme-linked immunosorbent assay (tube-ELISA) was developed and used to determine carbaryl (1-naphthyl methylcarbamate) residues in agricultural products (apple, Chinese cabbage, rice, and barley). The tube-ELISA is a competitive immunoassay in which the antibody is coated in the polystyrene tube, with a dynamic range between 0.7 and 46.3 μg kg^?1. Carbaryl was extracted from each agricultural sample by hand-shaking with methanol and examined for application to on-site analysis. After the liquid extraction, the sample extracts diluted with buffer were analyzed by rapid tube-ELISA directly. The overall test time was around 15–30 min, including sample preparation and assay performance. The results obtained from tube-ELISA correlated well with high-performance liquid chromatography (R ² > 0.9). The study shows that tube-ELISA is useful as a quality control tool and can be used to quantitatively detect carbaryl as well.     

Bioremediation of tributyltin contaminated sediment: degradation enhancement and improvement of bioavailability to promote treatment processes

Bioremediation of tributyltin (TBT) contaminated sediment was studied and degradation enhancement and improvement of bioavailability were also investigated. In TBT spiked sediment, the half-life of TBT in the control sample, representing natural attenuation, was 578 d indicating its persistence. In the stimulated sample (pH 7.5, aeration and incubated at 28 °C), the half-life was significantly reduced to 11 d. Further stimulation by nutrient addition (succinate, glycerol and l-arginine) or inoculation with Enterobacter cloacae (∼10⁷ viable cells g⁻¹ of sediment) resulted in half-life reduction to 9 and 10 d, respectively. In non-spiked sediment, the indigenous microorganisms were able to degrade aged TBT, but the extended period of contamination decreased the degradation efficiency. To improve bioavailability, addition of surfactant, adjustment of salinity and sonication were studied. The highest percentage solubilisation of TBT in water was obtained by adjusting salinity to 20 psu, which increased the solubility of TBT from 13% to 33%. Half-lives after bioavailability was improved were 5, 4 and 4 d for stimulation, stimulation w/nutrient addition and stimulation w/inoculation, respectively. However, natural attenuation in the control sample was not enhanced. The results show that providing suitable conditions is important in enhancing TBT biodegradation, and bioavailability improvement additionally increased the rate and degraded amount of TBT. Unfortunately, nutrient addition and inoculation of the degrader did not enhance the degradation appreciably.     

Solid chemosorbent for sampling sub-ppm levels of acrolein and glutaraldehyde in air

A personal air sampling method using Amberlite XAD-2 coated with 2,4-dinitrophenylhydrazine has been developed for acrolein and glutaral dehyde. Acrolein in the 0.01 to 1.2 mg/m³ range or glutaraldehyde in the 0.03 to 3.5 mg/m³ range is easily analysed in a 5 1 air sample. Recoveries are high (80–100%), and samples stable at least for two weeks if stored in the dark until analysed.     

Evaluation of Probes Used for Source Sampling of Hydrogen Fluoride

The body of information presented in this paper is directed to those individuals concerned with methods for the sampling and measurement of fluorides contained in stack gases produced during the manufacture of phosphate fertilizer or aluminum. An air stream containing gaseous hydrogen fluoride (HF), at concentrations of from 87 to 1700 µg F m^-3, was generated and passed through 193 to 198 cm lengths of Pyrex glass, type 316 stainless steel, TFE Teflon, and methyl methacrylate-coated aluminum probes at flow rates of 28 I min^-1. HF passing through the probes was collected in deionized water contained in a Greenburg-Smith impinger. The Teflon probe exhibited no loss of HF and no trend toward increased passage of HF with time. Significant amounts of fluoride were lost in 18 out of 20 tests with the methacrylate probe and in 4 out of 20 tests with the Pyrex and stainless steel probes. Trends toward increased passage of HF with time occurred with the latter three probe materials. The selective ion electrode and semiautomated methods gave equivalent results when samples were made alkaline to avoid sorption of fluoride by Tygon tubing used in the semiautomated method. These results demonstrated that a Teflon probe gave the most representative sample of gaseous HF. However, additional tests are needed before a final recommendation is made for a probe to sample fluorides in stack gases.     

Development of a real-time immuno-PCR assay for the quantification of 17β-estradiol in water

A competitive real-time (RT) immuno-polymerase chain reaction (iPCR) (RT-iPCR) assay was developed for the sensitive quantification of 17β-estradiol in water. Using a universal iPCR method and polyclonal antibodies, 17β-estradiol was accurately quantified at concentrations ranging from 1 pg mL^?1 to 10 µg mL^?1. The RT-iPCR assay's limit of detection was 0.7 pg mL^?1. The RT-iPCR assay provided an 800-fold increase in sensitivity as well as an expanded working range compared with the corresponding enzyme-linked immunosorbent assay. Assay cross-reactivity to estrone and estriol, two structurally related estrogens, was below 8%. Water samples spiked with 17β-estradiol were analyzed by RT-iPCR to determine the assay's potential as a rapid screen for the monitoring of manure-borne estrogens in the environment. The assay showed recoveries of 82, 102 and 103% for Milli-Q, tap, and irrigation water, respectively, without requiring sample extraction or concentration prior to analysis.     

Development of an enzyme-linked immunosorbent assay for atrazine monitoring in water samples

The implementation of the Water Framework Directive (2000/60/EC) requires the establishment of monitoring programs. However, conventional procedures for sample preparation prior to chromatographic analysis are rather expensive and time consuming, being the development of cost-effective and easy tool a necessity. The aim of this work was to develop an enzyme-linked immunosorbent assay (ELISA) able to determine atrazine in water samples. Matrix effects evaluation showed that the increase of humic acid (HA) concentration leads to flattened calibration curves and to the loss of the sigmoidal shape. However, such interference was overcome, by the presence of an environmental sample buffer, incubated together with the samples. Recoveries from 88.5 to 119.2 % were obtained in the presence of HA concentrations up to 20 mg?L^?1. An analytical range from 0.003 to 1 μg?L^?1 was obtained, and atrazine was detected in a sewage treatment plant with concentrations ranging from 14 to 52 ng?L^?1.     

Analysis of Organophosphorus Pesticides in Whole Milk by Solid Phase Microextraction Gas Chromatography Method

Solid phase microextraction (SPME) was used for the extraction of residual coumaphos and dichlorvos in whole milk. The residues were analyzed by capillary gas chromatography equipped with nitrogen phosphorus detector (GC-NPD). A manual SPME holder with a 100-μm polyacrylate fiber was used. The optimized conditions for extraction by SPME method were: sample agitation, absorption temperature of 30°C, absorption time of 40 min, desorption time of 10 min, and sample volume was 16.0 mL in the vial. Under these conditions, the calibration graphs were linear in the range of 0.17 μgL^?1 to 1.75 μgL^?1 for coumaphos and 0.69 μgL^?1 to 6.90 μgL^?1 for dichlorvos. Precision was good with RSD values of 13% for coumaphos and 14% for dichlorvos. The detection limits (LOD) were 0.060 μgL^?1 for dichlorvos and 0.052 for coumaphos. The quantification limits (LOQ) were 0.086 μgL^?1 for dichlorvos and 0.066 μgL^?1 for coumaphos. The results obtained in this study suggest that SPME is a suitable technique for residual pesticide analysis of milk. The data demonstrate that particular OP pesticides used in dairy farming in the region of Minas Gerais were found to contaminate cow whole milk, and the residues are not removed by treating the milk by boiling.     

Static secondary ion mass spectrometry as a new analytical tool for measuring atmospheric particles on insulating substrates

The paper presents static secondary ion mass spectrometry (S-SIMS) analyses of aerosol particles, which have been collected on an insulating polycarbonate filter (nuclepore) using a two-stage streaker sampler. A method was developed to analyze one streaker sample in its entirety without the need of cutting the filter. The latter allows the analysis of the same sample set with complementary techniques. Simultaneous detection of low Z atomic ions (Z<11) together with mean Z atomic ions (11<Z<82) and molecular fragment ions (e.g. HSO₄⁻,NO₂⁻,NH₄⁺) has shown to be feasible and has proven to be a major advantage of this technique. The large amounts of spectral data received were reduced by statistical clustering and were interpreted. A separate group of positive ions, e.g. Fe, K, Mn, Al, and Mg showed correlation with the PO₂ ion in the negative mode and were identified as particle emission from the steel plant. Practical problems of sample introduction and spectral effects due to charge compensation were solved and will be discussed. Despite the lack of quantitative analysis, static SIMS can be used to determine the relative abundance of compounds present in the sample and the correlation between them. In addition, the technique has been proven to provide complementary information to particle induced X-ray emission results of the same sample.     

Ion chromatographic determination of anions in rainwater

High acidity rainwater has recently become an issue in environmental pollution because of its great influence on ecological systems with special reference to the human environment. To solve this problem, the chemical behaviors of various pollutants in the air, particularly in the wet atmosphere must be studied. Ion chromatography was used for rapid analysis of trace amounts of anions.As a result, it was found that a combination of 2mM Na₂CO₃ and 5mM NaOH as an eluent was suitable for the separation of various anions. The reproducibility of determination of anions in standard solutions was found to be satisfactory with a coefficient of variation (CV) of 2–4% for F^?, Br^?, NO^?₃, SO^2?₃, SO^2?₄, and PO^3?₄, but not for NO^?₂. The determination of NO^?₂ was accomplished by preparing an eluent having almost the same composition and cencentration as that of the standard and sample solutions. The precision of the method with rainwater samples was less than 10%, and was considered to be usable for data analysis.In addition, a considerable number of ions in rainwater samples could be determined by using 1–3 ml of the sample without pretreatment. It was found that ion chromatography was one of the best means to obtain information on the chemical behaviors of trace amounts of anions in rainwater.     

Development,validation and matrix effect of a QuEChERS method for the analysis of organochlorine pesticides in fish tissue

This study aims to develop and validate a method to determine OCPs in fish tissues, minimizing the consumption of sample and reagents, by using a modified QuEChERS along with ultrasound, d-SPE and gas chromatography with an electron capture detector (GC-ECD), refraining the pooling. Different factorial designs were employed to optimize the sample preparation phase. The validation method presented a recovery of around 77.3% and 110.8%, with RSD lower than 13% and the detection limits were between 0.24 and 2.88 μgkg^?1, revealing good sensitiveness and accuracy. The method was satisfactorily applied to the analysis of tissues from different species of fish and OCPs residues were detected. The proposed method was shown effective to determine OCPs low concentrations in fish tissues, using small sample mass (0.5 g), making the sample analyses viable without the need for grouping (pool).     

Dry deposition of ozone on building materials. Chamber measurements and modelling of the time-dependent deposition

Tests of the dry deposition of ozone to the surfaces of a concrete floor tile and an activated carbon cloth (ACC) sample were performed in a deposition chamber. The time-dependent deposition of ozone to the material surfaces was modelled with an adsorption, desorption, reaction model. This made it possible to find deposition velocities at equilibrium, at t=∞, from shorter time runs of 48 h. The total equilibrium deposition velocity on the concrete floor tile was found to decrease from 0.08(10) to 0.057(10) cm s⁻¹ in three consecutive runs on the same sample, and was found to be 0.137(8) cm s⁻¹ on an ACC. All at a linear airflow velocity of 0.092 cm s⁻¹, RH=50% and T=22°C. Varying the airflow in the deposition chamber, the surface deposition velocity was found to equal to the total deposition velocity for the concrete floor tile. A surface deposition velocity of 0.186(8) cm s⁻¹ was found for the ACC sample. The total real area and the reaction rate constant for the decomposition of ozone was found to be larger, and the adsorption rate constant, the desorption rate constant and the mass of ozone on the surface smaller, on the ACC sample than on the concrete floor tile.     

Structure of the major metabolite of 5-ethyl-2′-deoxyuridine in rats

The major metabolite of 5-ethyl-2′-deoxyuridine in rats has been isolated and purified by preparative thick layer and column chromatography. By mass and ¹H NMR spectroscopy, it was identified as 5-(1-hydroxyethyl) uracil; the structure was confirmed by comparison with an authentic sample.     

Water pressure head and temperature impact on isoxaflutole degradation in crop residues and loamy surface soil under conventional and conservation tillage management

Laboratory incubations were performed in order to evaluate the dissipation of the proherbicide isoxaflutole in seedbed layer soil samples from conventional and conservation tillage systems and in maize and oat residues left at the soil surface under conservation tillage. The effects of temperature and water pressure head on radiolabelled isoxaflutole degradation were studied for each sample for 21 d. Mineralisation of isoxaflutole was low for all samples and ranged from 0.0% to 0.9% of applied ¹⁴C in soil samples and from 0.0% to 2.4% of applied ¹⁴C in residue samples. In soil samples, degradation half-life of isoxaflutole ranged from 9 to 26 h, with significantly higher values under conservation tillage. In residue samples, degradation half-life ranged from 3 to 31 h, with significantly higher values in maize residues, despite a higher mineralisation and bound residue formation than in oat residues. Whatever the sample, most of the applied ¹⁴C remained extractable during the experiment and, after 21 d, less than 15% of applied ¹⁴C were unextractable. This extractable fraction was composed of diketonitrile, benzoic acid derivative and several unidentified metabolites, with one of them accounting for more than 17% of applied ¹⁴C. This study showed that tillage system design, including crop residues management, could help reducing the environmental impacts of isoxaflutole.     

Determination of soil content in chlordecone (organochlorine pesticide) using near infrared reflectance spectroscopy (NIRS)

Chlordecone is a toxic organochlorine insecticide that was used in banana plantations until 1993 in the French West Indies. This study aimed at assessing the potential of near infrared reflectance spectroscopy (NIRS) for determining chlordecone content in Andosols, Nitisols and Ferralsols from Martinique. Using partial least square regression, chlordecone content conventionally determined through gas chromatography–mass spectrometry could be correctly predicted by NIRS (Q² = 0.75, R² = 0.82 for the total set), especially for samples with chlordecone content <12 mg kg⁻¹ or when the sample set was rather homogeneous (Q² = 0.91, R² = 0.82 for the Andosols). Conventional measures and NIRS predictions were poorly correlated for chlordecone content >12 mg kg⁻¹, nevertheless ca. 80% samples were correctly predicted when the set was divided into three or four classes of chlordecone content. Thus NIRS could be considered a time- and cost-effective method for characterising soil contamination by chlordecone.     

Fate of the veterinary antibiotic 14C-difloxacin in soil including simultaneous amendment of pig manure with the focus on non-extractable residues

The fate of ¹⁴C-labeled difloxacin (¹⁴C-DIF) was studied in time course experiments after application on soil (Ap horizon of silt loam) and amendment of authentic DIF containing pig manure (146 mL kg^?1; 4.17 MBq kg^?1; 0.85 mg kg^?1) or water (124 mL kg^?1; 0.42 MBq kg^?1; 0.09 mg kg^?1) for 56 and 120 days of incubation, respectively.

Mineralization of ¹⁴C-DIF was below 0.2% in both experiments after 56 days or 120 days. In the course of the experiments, portions of extractable radioactivity (Accelerated Solvent Extraction (ASE); acetonitrile-water) decreased to 19–21% depending only little on manure amendment. Non-extractable residues of ¹⁴C-DIF increased to 70–74% after 56 days and 120 days, respectively, and therefore were the main route of ¹⁴C-DIF in soil. According to radioanalytical HPLC and LC-MS/MS, only the parent compound was found in all extracts over the whole time of the experiment. According to fractionation of the non-extractable residues (NER) into particle size fractions, ¹⁴C portions were associated to the water used for fractionation, the silt and clay fractions, whereas no radioactivity was detected in the sand fraction. The majority of ¹⁴C was found within the clay fractions.

Fractionation of humic components showed that radioactivity derived from ¹⁴C-DIF was associated with humic acids, fulvic acids, humins and minerals and very little with soluble, non-humic HCl fraction. The highest portions of radioactivity were found in the fulvic acid fraction. Results obtained by size exclusion chromatography (SEC) of the purified fulvic acids were similar for every sample analyzed. One large portion of ¹⁴C co-eluted with fulvic acids of a molecular weight below 910 g mol^?1. Both fractionation methods demonstrated that the parent compound DIF or initial metabolites were rapidly integrated into humic materials and, thus, were major components of NER.     

Application of an ELISA to the quantification of carbamazepine in ground, surface and wastewaters and validation with LC-MS/MS

Carbamazepine is a psychiatric pharmaceutical widely detected in aquatic environments. Due to its generalized occurrence and environmental persistence it might be considered as an anthropogenic pollution indicator. In this research, a previously developed enzyme-linked immunosorbent assay (ELISA), based on a commercial monoclonal antibody, was applied to the quantification of carbamazepine in ground, surface and wastewaters and results were validated by liquid chromatography-tandem mass spectrometry (LC-MS/MS).The performance of the applied ELISA methodology was tested in the presence of high concentrations of sodium chloride and dissolved organic matter. The method was not significantly affected by matrix effects, being adequate for the quantification of carbamazepine in environmental samples, even without sample pre-treatment. This method allows the quantification of carbamazepine in the range of 0.03-10 μg L⁻¹, with a relative error lower than 30%. Due to a pH dependent cross-reactivity with cetirizine, an antihistaminic drug, the assay also enabled the quantification of cetirizine in the samples.The application of the developed method to the quantification of carbamazepine was performed by using environmental samples with very different matrices, collected in the geographical area of Ria de Aveiro, an estuarine system located in the North of Portugal. Carbamazepine was detected in all analyzed wastewater samples and in one surface water with concentrations between 0.1 and 0.7 μg L⁻¹. Validation with LC-MS/MS revealed that results obtained by ELISA are 2-28% overestimated, which was considered highly satisfactory due to the absence of sample pre-treatments.     

FTIR transmission spectrometry for the nondestructive determination of ammonium and sulfate in ambient aerosols collected on teflon filters

Fourier transform infrared (FTIR) transmission spectrometry has been used to determine ammonium and sulfate in ambient aerosol particles collected on Teflon filters. Integrated absorbance as well as maximum absorbance values for ammonium and sulfate are linearly related to X-ray fluorescence measurements of total sulfur. Apparent detection limits of 1.4 μg m⁻³ for sulfate and 0.5 μg m⁻³ for ammonium (for sample volumes of 21.6 m³) were estimated for samples from Topeka, Kansas; Portage, Wisconsin; Steubenville, Ohio; and Charlottesville, Virginia. The apparent detection limits were essentially independent of sample loading over the range of 0–20 μg m⁻³ of total sulfur. The FTIR transmission measurements of these samples are very precise e.g. repetitive measurements vary ± 0.2% and blank variability is 0.13 μg m⁻³ and 0.20 μg m⁻³ in terms of sulfate and ammonium, respectively. Contributions to analytical uncertainty include 5–8% uncertainties in X-ray fluorescence measurements for total sulfur and the influence of unspecified site-dependent sample characteristics. The method offers the significant advantages of nondestructive analysis, no sample preparation, molecular speciation and rapid analysis.     

Simultaneous determination of pesticides,mycotoxins, tropane alkaloids,growth regulators,and pyrrolizidine alkaloids in oats and whole wheat grains after online clean-up via two-dimensional liquid chromatography tandem mass spectrometry

In this study, a two-dimensional liquid chromatography tandem mass spectrometry method was developed and validated for the determination of pesticide residues and contaminants in whole wheat grains and oats. The samples were extracted with a mixture of acetonitrile and water and were injected into the two-dimensional LC-MS/MS system without any further clean-up or sample preparation. Samples were analyzed with four different matrix matched calibrations. Matrix effects were evaluated by comparing analyte signals in the respective matrix matched standard with the neat solvent standards. The final method was validated according to the current Eurachem validation guide and SANTE document. The number of successfully validated analytes throughout all three validation levels in oats and wheat, respectively, were as follows: 330 and 316 out of 370 pesticides, 6 and 13 out of 18 pyrrolizidine alkaloids and 7 out of 9 regulated mycotoxins. Moreover, both plant growth regulators mepiquat and chlormequat as well as the tropane alkaloids atropine and scopolamine met the validation criteria. The majority of pesticides showed limits of detection below 1?µg kg^?1, pyrrolizidine alkaloids below 0.7?µg kg^?1, tropane alkaloids below 0.2?µg kg^?1, growth regulators below 0.7?µg kg^?1 and mycotoxins below 8?µg kg^?1 in both matrices.     

Bioremediation of strontium (Sr) contaminated aquifer quartz sand based on carbonate precipitation induced by Sr resistant Halomonas sp

Contamination of aquifers or sediments by radioactive strontium (⁹⁰Sr) is a significant environmental problem. In the present study, microbially induced calcite precipitation (MICP) was evaluated for its potential to remediate strontium from aquifer quartz sand. A Sr resistant urease producing Halomonas sp. was characterized for its potential role in bioremediation. The bacterial strain removed 80% of Sr from soluble-exchangeable fraction of aquifer quartz sand. X-ray diffraction detected calcite, vaterite and aragonite along with calcite-strontianite (SrCO₃) solid solution in bioremediated sample with indications that Sr was incorporated into the calcite. Scanning electron micrography coupled with energy-dispersive X-ray further confirmed MICP process in remediation. The study showed that MICP sequesters soluble strontium as biominerals and could play an important role in strontium bioremediation from both ecological and greener point of view.