Determination of Endocrine Disrupting Chemicals in Water and Wastewater Samples by Liquid Chromatography-Negative Ion Electrospray Ionization-Tandem Mass Spectrometry.

A liquid chromatography-negative ion electrospray ionization-tandem mass spectrometry method was developed for the simultaneous analysis of bisphenol A, 4-octylphenol, 4-nonylphenol, diethylstilbestrol, 17ß-estradiol, estriol, estrone, 17α-ethinylestradiol, prednisone, and prednisolone. This method used solid-phase extraction with an elution solvent of acetonitrile to improve the stability of the analytes. To maintain the stability of analytes analyses were completed within five days. The recoveries ranged from 84 to 112% and the relative standard deviation of analysis of duplicate samples was <10%. The limits of quantitation were 1-10 ng/L. Surface water and wastewater were obtained from five wastewater treatment plants in Saskatchewan. Matrix effects were moderate to severe. Using standard addition calibration, all analytes except diethylstilbestrol and 17α-ethinyl estradiol were detected. There was a low frequency of detection of the target analytes in upstream and downstream water, indicating good removal efficiency during the wastewater treatment process. Bisphenol A and 4-nonylphenol were the only analytes detected downstream. Bisphenol A was the most frequently detected in raw wastewater (133 to 403 ng/L). Estriol was detected more often in raw wastewater than estrone or 17ß-estradiol. This is the first Canadian study with the detection of prednisone and prednisolone with concentrations at 198-350 ng/L in raw wastewater at 60% of the wastewater treatment plants.

Insights into Long-Term Toxicity of Triclosan to Freshwater Green Algae in Lake Erie.

This study explored the long-term impacts of a pulse disturbance of triclosan on five nontarget green algae in Lake Erie. Comprehensive analyses were performed using multiple physiological end points at community and subcellular scales. The toxic mechanism of triclosan in a wide range of concentrations was analyzed. The diverse sensitivity of algae species and complex interrelationships among multiple end points were revealed. The results showed the taxonomic groups of algae were the key issue for sensitivity difference. High doses of triclosan caused irreversible damage on algae, and environmentally relevant doses initiated either inhibition or stimulation. Smaller cells had higher sensitivity to triclosan, while larger cells had a wider size variation after exposure. Colonial cells were less sensitive than unicells. For chlorophyll, there were better dose-response relationships in Chlorococcum sp., Chlamydomonas reinhardtii CPCC 12 and 243 than Asterococcus superbus and Eremosphaera viridis. For chlorophyll fluorescence, Fv/ Fm was the most sensitive parameter, and qN was more sensitive than qP. Triclosan showed long-term effects on biochemical components, such as lipids, proteins, and nucleic acids. The findings will be helpful for a systematic and complete assessment of triclosan toxicity in natural waters and the development of appropriate strategies for its risk management.

Pressurized Solvent Extraction with Ethyl Acetate and Liquid Chromatography-Tandem Mass Spectrometry for the Analysis of Selected Conazole Fungicides in Matcha.

The extraction of powdered nutraceuticals is challenging due to the low water content and high concentration of matrix components that can lead to significant matrix effects in liquid chromatography-positive ion electrospray ionization-tandem mass spectrometry (LC-ESI⁺-MS/MS). In this study we assess the feasibility of using pressurized solvent extraction with ethyl acetate to reduce the co-extraction of polar matrix components. Pigment attributed to chlorophyll was removed with in-cell clean-up utilizing Anasorb 747, Florisil®, and C18. Visible inspection of the extracts showed that pigment was removed from matcha, a powdered green tea sample. Pressurized solvent extraction with in-cell clean-up can be utilized to remove pigments from powdered samples such as nutraceuticals. Average matrix effect of the 32 target analytes that observed mass spectrometric signal suppression or soft MS signal enhancement was -41 ± 19% with the majority of analytes having a protonated molecular ion with m/z of 250 to 412. As generally moderate signal suppression was observed for conazole fungicides and structurally related compounds analyzed by LC-ESI⁺-MS/MS, it is recommended that matrix matched or standard addition calibration is used for quantitation. Catachins, other polyphenols, and caffeine are expected to contribute to the matrix effects observed in LC-ESI⁺-MS/MS. Diniconazole, fenbuconazole, and tebufenozide were the only target analytes with severe MS signal enhancement. Low levels (0.002⁻0.004 mg/kg) of prothioconazole-desthio and flusilazole were detected, along with trace levels of tebuthiuron in matcha.

New Trends in Pesticide Residue Analysis in Cereals, Nutraceuticals, Baby Foods, and Related Processed Consumer Products.

Pesticide residue methods have been developed for a wide variety of food products including cereal-based foods, nutraceuticals and related plant products, and baby foods. These cereal, fruit, vegetable, and plant-based products provide the basis for many processed consumer products. For cereal and nutraceuticals, which are dry sample products, a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method has been used with additional steps to allow wetting of the dry sample matrix and subsequent cleanup using dispersive or cartridge format SPE to reduce matrix effects. More processed foods may have lower pesticide concentrations but higher co-extracts that can lead to signal suppression or enhancement with MS detection. For complex matrixes, GC/MS/MS or LC/electrospray ionization (positive or negative ion)-MS/MS is more frequently used. The extraction and cleanup methods vary with different sample types particularly for cereal-based products, and these different approaches are discussed in this review. General instrument considerations are also discussed.

Determination of neonicotinoid insecticides and strobilurin fungicides in particle phase atmospheric samples by liquid chromatography-tandem mass spectrometry.

A liquid chromatography-tandem mass spectrometry method has been developed for the determination of neonicotinoids and strobilurin fungicides in the particle phase fraction of atmosphere samples. Filter samples were extracted with pressurized solvent extraction, followed by a cleanup step with solid phase extraction. Method detection limits for the seven neonicotinoid insecticides and six strobilurin fungicides were in the range of 1.0-4.0 pg/m(3). Samples were collected from June to September 2013 at two locations (Osoyoos and Oliver) in the southern Okanagan Valley Agricultural Region of British Columbia, where these insecticides and fungicides are recommended for use on tree fruit crops (apples, pears, cherries, peaches, apricots) and vineyards. This work represents the first detection of acetamiprid, imidacloprid, clothianidin, kresoxim-methyl, pyraclostrobin, and trifloxystrobin in particle phase atmospheric samples collected in the Okanagan Valley in Canada. The highest particle phase atmospheric concentrations were observed for imidacloprid, pyraclostrobin, and trifloxystrobin at 360.0, 655.6, and 1908.2 pg/m(3), respectively.

Effects of a herbicide mixture on primary and bacterial productivity in four prairie wetlands with varying salinities: an enclosure approach.

Wetlands in the Prairie pothole region of Saskatchewan and Manitoba serve an important role in providing wildlife habitat, water storage and water filtration. They display a wide range of water quality parameters such as salinity, nutrients and major ions with sulfate as the dominant ion for the most saline wetlands. The differences in these water quality parameters among wetlands are reflected in the composition of aquatic plant communities and their productivity. Interspersed within an intensely managed agricultural landscape where pesticides are commonly used, mixtures of herbicides are often detected in these wetlands as well as in rivers, and drinking water reservoirs. One freshwater and three wetlands of varying salinity in the St. Denis National Wildlife Area, Saskatchewan, Canada were selected to study the effects of a mixture of eight herbicides (2,4-D, MCPA, dicamba, clopyralid, bromoxynil, mecoprop, dichlorprop, and glyphosate) on wetland microbial communities using an outdoor enclosure approach. Six enclosures (three controls and three treatments) were installed in each wetland and the herbicide mixture added to the treatment enclosures. The concentration of each herbicide in the enclosure water was that which would have resulted from a direct overspray of a 0.5-m deep wetland at its recommended field application rate. After herbicide addition, primary and bacterial productivity, and algal biomass were measured in both planktonic and benthic communities over 28 days. The herbicide mixture had a stimulatory effect on primary productivity in the nutrient-sufficient freshwater wetland while no stimulatory effect was observed in the nutrient-deficient saline wetlands. The differences observed in the effects of the herbicide mixture appear to be related to the nutrient bioavailability in these wetlands.

A review of methods for the analysis of orphan and difficult pesticides: glyphosate, glufosinate, quaternary ammonium and phenoxy acid herbicides, and dithiocarbamate and phthalimide fungicides.

This article reviews the chromatography/MS methodologies for analysis of pesticide residues of orphan and difficult chemical classes in a variety of sample matrixes including water, urine, blood, and food. The review focuses on pesticide classes that are not commonly included in multiresidue analysis methods such as highly polar or ionic herbicides including glyphosate, glufosinate, quaternary ammonium, and phenoxy acid herbicides, and some of their major degradation or metabolite products. In addition, dithiocarbamate and phthalimide fungicides, which are thermally unstable and have stability issues in some solvents or sample matrixes, are also examined due to their special needs in residue analysis.