Occurrence of Natural and Synthetic Glucocorticoids in Sewage Treatment Plants and Receiving River Waters

This paper first reports the occurrence of six glucocorticoids (prednisone, prednisolone, cortisone, cortisol, dexamethasone, and 6α-methylprednisolone) in sewage treatment plants (STPs) and receiving rivers by establishing a method for analyzing glucocorticoids in complex environmental waters. For the various types of aqueous matrices considered, the absolute recoveries were from 73 to 99%, and limits of quantification were below 0.2 ng/L. Among the seven STPs studied, the average concentrations of prednisone, prednisolone, cortisone, cortisol, dexamethasone, and 6α-methylprednisolone in influents were, respectively, 2.6 ± 2.1, 3.0 ± 1.6, 30 ± 21, 39 ± 26, 1.2 ± 0.70, and 0.62 ± 0.65 ng/L, and their percent removals were 99 ± 3.1, 78 ± 8.8, 99 ± 1.2, 98 ± 2.5, 99 ± 1.8, and 100 ± 0%, respectively. The lower removal of prednisolone was found to be due to its relatively low efficiency of biodegradation, especially in anoxic and aerobic units. The frequently detected glucocorticoids in effluents were prednisolone, cortisol, and cortisone with average concentrations 0.56 ± 0.06, 0.50 ± 0.33, and 0.26 ± 0.10 ng/L. In the receiving waters, the Tonghui and Qing Rivers, the concentrations of these compounds in some samples were much higher than those in their corresponding STP effluents; these differences depended on the sampling date, suggesting that there was random discharging of untreated wastewaters into these rivers. In addition, the ratio between the combined concentrations of two natural glucocorticoids (cortisol and cortisone) and the concentration of one synthetic glucocorticoid, prednisolone, was found to be a potential index to reflect the wastewater discharging

Analysis of Bisphenol A and Alkylphenols in Cereals by Automated On-line Solid-Phase Extraction and Liquid Chromatography Tandem Mass Spectrometry

An on-line solid-phase extraction (SPE) following a liquid chromatography–electrospray ionization–tandem mass spectrometry (LC–ESI–MS/MS) method was established for the simultaneous analysis of bisphenol A (BPA), nonylphenol (NP), and octylphenol (OP) in cereals (including rice, maize, and wheat). The target compounds were extracted by acetonitrile, purified by an automated on-line SPE cartridge, and analyzed by LC–MS/MS under the negative-ion mode. Mean recoveries fortified at three concentration levels ranged from 81.6 to 115.7%, and the coefficient of variation ranged from 4.6 to 19.9% (<i>n</i> = 6). The limits of quantification (LOQs) of the method were 0.5, 0.5, and 0.25 μg/kg for BPA, NP, and OP, respectively, in both rice and maize, while the LOQs in wheat were 0.5, 1.25, and 0.5 μg/kg for BPA, NP, and OP, respectively. This method was applied in the analysis of rice, maize, and wheat from a local market. As a result, NP occurred in all cereal samples at the concentration range of 9.4–1683.6 μg/kg and BPA was detected in a few samples

Natural Occurrence of Four Alternaria Mycotoxins in Tomato- and Citrus-Based Foods in China

A total of 70 tomato-based and 86 citrus-based products collected in China were analyzed for alternariol, alternariol monomethyl ether, tentoxin, and tenuazonic acid by ultraperformance liquid chromatography–electrospray ionization–tandem mass spectrometry. No toxins were found in any fresh tomato or citrus fruit samples. Tenuazonic acid was the predominant toxin detected in all tomato ketchup (10.2–1787 μg/kg) and tomato juice samples (7.4–278 μg/kg). Alternariol was quantitated at higher level than alternariol monomethyl ether with the ratio of alternariol/alternariol monomethyl ether ranging from 0.37 to 104 in 14 alternariol-positive tomato ketchup samples. Tentoxin was detected at much lower levels in all samples analyzed. Some citrus juice samples were positive for tenuazonic acid and alternariol monomethyl ether. It is necessary to conduct a systemic surveillance of <i>Alternaria</i> toxins in raw and processed foods to provide the scientific basis for risk assessment of dietary exposure to these toxins in Chinese populations

Simultaneous Determination of 25 Ergot Alkaloids in Cereal Samples by Ultraperformance Liquid Chromatography–Tandem Mass Spectrometry

A liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) method was developed and validated for the simultaneous determination of 25 ergot alkaloids in cereal samples. The analytes included both -ine and -inine ergot alkaloids and were extracted using an acetonitrile and ammonium carbonate solution, followed by purification with C-18 sorbent. After full separation on a C18 column, the 25 ergot alkaloids were detected by LC-MS/MS using multiple reaction monitoring (MRM) in the positive ion mode. The linear range was 0.05–5.0 μg/kg for the 25 ergot alkaloids. The mean recoveries at three spiked concentrations varied from 76.5 to 120% with RSD < 15%. This method was validated using a FAPAS proficiency test sample of ergot alkaloids in rye flour and was finally applied to analyze real samples, including rye flours, wheat flours, whole wheat flours, bread, and noodles

Hairy and Bnl control terminal cell lumen length.

<p>Graph showing lumen length of terminal branches in wild-type embryos, <i>h⁶⁷⁴</i> and <i>h⁴⁷</i> homozygous embryos, <i>bnl^P2</i> heterozygous embryos and <i>h⁶⁷⁴</i>homozygous embryos with one copy of <i>bnl^P2</i>. n =  number of terminal branches scored. Values are means ± S.D. <i>P</i><0.001.</p

Terminal cell specification by activated breathless is enhanced by loss of hairy.

<p>Lateral trunks of wild-type embryos (A) contain approximately five terminal cells (TCs) whereas lateral trunks of trachea expressing activated breathless (<i>btl^ACT</i>) with <i>btl</i>-GAL4 (B) and <i>btl^ACT</i> expressing trachea of <i>h²²</i> heterozygous embryos (C) contain more TCs in the lateral trunk branches. Graph shows Hairy-dependent increase in TC specification by activated Btl in metameres 2–9; n represents number of embryos scored (D). In <i>h⁶⁷⁴</i> heterozygous embryos (E), each dorsal branch has two cells expressing <i>btl</i> RNA whereas in homozygous siblings (F), each dorsal branch has two or more cells expressing <i>btl</i> RNA. Embryos in A–C were stained for DSRF (red), Piopio (blue) to label the tracheal lumen and β-gal (not shown). Panels A–C are lateral views of projected confocal images. Embryos in E and F were hybridized <i>in situ</i> for <i>btl</i> RNA (purple) and <i>trachealess</i> RNA (pink). Scale bar in A represents 20 µm.</p

Time-Resolved Fluoroimmunoassay as an Advantageous Approach for Highly Efficient Determination of Sulfonamides in Environmental Waters

Using monoclonal antibodies labeled with Eu3+ chelates, time-resolved fluoroimmunoassay (TRFIA) methods were developed for the determination of trace sulfamethazine (SMZ), sulfa-methoxazole (SMX), and sulfadiazine (SDZ) in environmental waters. Under the optimized conditions, the developed methods offered (i) low detection limits (9.8 ng/L SMZ, 6.1 ng/L SMX, and 5.4 ng/L SDZ, based on 90% inhibition) which were about 1 order of magnitude lower than that of the enzyme-linked immunosorbent assay (ELISA), (ii) high selectivity with no cross-reactivity (2+, Cd2+, Hg2+, Pb2+, and As(V)) in the samples, and (iv) direct determination with low cost, high sample throughput, and low sample consumption (50−100 μL). The proposed TRFIA procedures were applied to determine sulfonamides in a variety of surface water and wastewater samples without sample pretreatment other than filtration. The satisfactory recoveries (64−127%) and reproducibilities (CV = 0.2−16%) achieved, as well as the good agreement with those given by liquid chromatography−tandem mass spectroscopy and ELISA methods, demonstrated the applicability of the proposed TRFIA methods for routine screening/quantification of sulfonamides in environmental waters

Tracheal development is defective in <i>hairy</i> mutant embryos.

<p>In <i>h²²</i> heterozygous embryos, the dorsal trunk (DT) is a continuous tube (A, arrow) whereas in <i>h²²</i> (B) and <i>h⁶⁷⁴</i> (C) homozygous embryos, the DT is broken (B and C, arrows). In <i>h²²</i> heterozygous embryos (D and G), tracheal cells migrate to form six primary branches (D and G, arrows). In <i>h²²</i> (E and H) and <i>h⁶⁷⁴</i> (F and I) homozygous embryos, tracheal cells fail to migrate out (E, F, H and I, arrows). Embryos in panels A, B and C were double stained for 2A12 and β-galactosidase (β-gal) to distinguish heterozygous from homozygous siblings. Embryos in panels D to F were stained for Crumbs (Crb) to label the lumen and β-gal (not shown), and embryos in panels G to I were stained for Crb (white), β-gal (not shown) and Trachealess (Trh) (red) to label tracheal nuclei. Panels in D to I are projections of confocal sections of laterally viewed embryos. Scale bars in D and G represent 10 µm.</p

expression of <i>bnl</i> in the mesoderm phenocopies <i>hairy</i> mutant phenotype by specifying extra terminal cells.

<p>In stage 13 wild-type embryos (A and A'), <i>bnl</i> RNA is expressed in clusters surrounding the migrating trachea (A, arrow) and to a lesser extent in the circular visceral mesoderm (A', arrowhead). In stage 13 embryos where <i>bnl</i> is overexpressed with <i>twi</i>-GAL4 <i>mef2</i>-GAL4 (B), <i>bnl</i> RNA is expressed in the somatic mesoderm (B, arrowhead). In stage 13 embryos where <i>bnl</i> is expressed with <i>5053</i>-GAL4 (C and C'), <i>bnl</i> RNA is expressed in clusters close to the tracheal cells (C, arrow) and in longitudinal muscle founder cells of the visceral mesoderm (C' arrowheads). In stage 16 embryos expressing <i>bnl</i> with <i>5053</i>-GAL4 (D), <i>bnl</i> RNA is expressed in the ventral oblique lateral body wall muscles (D, arrowhead). In wild-type embryos (E), a single terminal cell (TC) is specified at the tip of each dorsal branch (E, arrow). In embryos overexpressing <i>bnl</i> in the entire mesoderm with <i>twi</i>-GAL4 <i>mef2</i>-GAL4 (F) or in a subset of the mesoderm with <i>5053</i>-GAL4 (G), extra TCs are specified in the dorsal branches (F and G, arrows). In wild-type embryos (H), a distinct number of TCs are specified in the lateral trunks (H, arrows) and the ganglionic branch (H, arrowhead) whereas in embryos expressing <i>bnl</i> in the mesoderm with either <i>twi</i>-GAL4 <i>mef2</i>-GAL4 (I) or <i>5053</i>-GAL4 (J) extra TCs in the lateral trunks (I and J, arrows) and ganglionic branches (J, arrowheads) are specified. Embryos in A–D were hybridized <i>in situ</i> with <i>bnl</i> RNA. Embryos in E–J were stained for DSRF (red) and 2A12 (green). All panels shown are lateral views except panel G which is a dorsal-lateral view. Scale bar in E represents 10 µm.</p

Pointed is epistatic to Hairy in terminal cell specification.

<p>In WT embryos (A), a single TC is specified in each dorsal branch (A, arrows), whereas dorsal branches of <i>pnt^Δ88</i> homozygous embryos lack TCs (*, B). In embryos overexpressing wild-type <i>pnt</i> in the entire trachea with <i>btl</i>-GAL4 (C), extra TCs are specified in all tracheal branches (C, arrows), including the dorsal trunk (C, arrowhead). Dorsal branches of embryos homozygous for both <i>h⁶⁷⁴</i> and <i>pn^Δ88</i> lack TCs (*, D). (E) Graph shows number of TCs per dorsal branch in metameres 2–9 in WT, <i>h⁶⁷⁴</i> and <i>pnt^Δ88</i> mutant embryos; n represents number of embryos scored. (F) Graph shows percentage of dorsal branches with various numbers of <i>pnt</i> RNA expressing cells; n represents number of embryos scored. <i>h⁶⁷⁴</i> heterozygous embryos (G) have a single dorsal branch cell expressing <i>pnt</i> RNA (G), whereas homozygous siblings have extra dorsal branch cells expressing <i>pnt</i> RNA (H). Embryos shown in panels A–D were stained for DSRF (red), 2A12 (green) and β-gal (not shown). Embryos shown in G and H were hybridized <i>in situ</i> for <i>pnt</i> RNA (purple) and <i>lac-Z</i> (not shown). Scale bar in A represents 20 µm.</p