Measurements of hydrocortisone and cortisone for longitudinal profiling of equine plasma by liquid chromatography-tandem mass spectrometry.

The conventional detection of exogenous drugs in equine doping samples has been used for confirmation and subsequent prosecution of participants responsible. In recent years, alternative methods using indirect detection have been investigated due to the expanding number of pharmaceutical agents available with the potential of misuse. The monitoring of endogenous biomarkers such as hydrocortisone (HC) has been studied in equine urine with an international threshold of 1 µg/ml established; however, there is no current threshold for equine plasma. The aim of this research was to investigate plasma concentrations of HC and cortisone (C) in race day samples compared to an administration of Triamcinolone Acetonide (TACA). The reference population (n = 1150) provided HC (6 to 145 ng/ml) and C (0.7 to 13 ng/ml) levels to derive the HC to C ratio (HC/C). Population reference limits (PRLs) were proposed for HC/C values at 0.2 (lower) and 61 (upper). Administration of TACA resulted in down-regulation of HC/C values below the estimated PRLs for up to 96 h post-administration. This indirect detection period was longer than the detection of TACA for 72 h. The use of individual reference limits (IRLs) for HC/C values was investigated to support the Equine Biological Passport (EBP), an intelligence model developed by Racing NSW for longitudinal monitoring of biomarkers.

Photocatalysis of estrone in water and wastewater: Comparison between Au-TiO2 nanocomposite and TiO2, and degradation by-products.

Gold-modified TiO2 (Au-TiO2) photocatalysts were utilised for the degradation of estrone (E1), a major endocrine disrupting chemical in water and wastewater. Au-TiO2 catalysts were synthesised by a deposition-precipitation method with gold loadings of 0-8% (wt%). The Au-TiO2 nanocomposite exhibited superior activity compared to P25 TiO2 under UVA (λ=365nm), cool white (λ>420nm) and green (λ=523nm) light emitting diodes (LEDs), for treating 1mgl-1 of E1. The 4wt% Au loading was found to produce the best photocatalytic activity with a rate constant of 2.44±0.36h-1, compared to 0.06±0.01h-1 for P25 TiO2, under visible light. In total 4 by-products were identified, one from negative ionization mode (m/z=269) and three from positive ionization mode (m/z=287) during photocatalysis, which were also degraded with time by Au-TiO2. For different water matrices, the photodegradation rate of E1 decreased in the order: ultrapure water>synthetic wastewater≈wastewater effluent from membrane bio-reactor. Overall, 4wt% Au-TiO2 demonstrated superior performance compared to P25 TiO2 in water and wastewater.

Chloramphenicol interaction with functionalized biochar in water: sorptive mechanism, molecular imprinting effect and repeatable application.

Biochar and functionalized biochar (fBC-1 and fBC-2) were prepared and applied to remove antibiotic chloramphenicol from deionized water, lake water and synthetic wastewater. Results showed that chloramphenicol removal on biochar was pH dependent and maximum sorption occurred at pH4.0-4.5. The sorption data of chloramphenicol fitted better with the Langmuir isotherm model than the Freundlich isotherm model with the maximum Langmuir sorption capacity of 233µMg-1 using fBC-2. Chloramphenicol sorption on fBC-2 followed the trend: deionized water>lake water>synthetic wastewater. The presence of humic acid decreased the sorption distribution coefficient (Kd) while the presence of low ionic strength and soil in solution increased Kd value significantly. The mechanism of sorption on fBC mainly involved electron-donor-acceptor (EDA) interactions at pH<2.0; formation of charge assisted hydrogen bond (CAHB) and hydrogen bonds in addition to EDA in the pH4.0-4.5; and CAHB and EDA interactions at pH>7.0. Additionally, solvent and thermal regeneration of fBC-2 for repeatable applications showed excellent sorption of chloramphenicol under the same condition, due to the creation of a molecular imprinting effect in fBC-2. Consequently, fBC-2 can be applied with excellent reusability properties to remove chloramphenicol and other similar organic contaminants.

Photodegradation of estrogenic endocrine disrupting steroidal hormones in aqueous systems: Progress and future challenges.

This article reviews different photodegradation technologies used for the removal of four endocrine disrupting chemicals (EDCs): estrone (E1), 17ß-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2). The degradation efficiency is greater under UV than visible light; and increases with light intensity up to when mass transfer becomes the rate limiting step. Substantial rates are observed in the environmentally relevant range of pH7-8, though higher rates are obtained for pH above the pKa (~10.4) of the EDCs. The effects of dissolved organic matter (DOM) on EDC photodegradation are complex with both positive and negative impacts being reported. TiO2 remains the best catalyst due to its superior activity, chemical and photo stability, cheap commercial availability, capacity to function at ambient conditions and low toxicity. The optimum TiO2 loading is 0.05-1gl(-1), while higher loadings have negative impact on EDC removal. The suspended catalysts prove to be more efficient in photocatalysis compared to the immobilised catalysts, while the latter are considered more suitable for commercial scale applications. Photodegradation mostly follows 1st or pseudo 1st order kinetics. Photodegradation typically eradicates or moderates estrogenic activity, though some intermediates are found to exhibit higher estrogenicity than the parent EDCs; the persistence of estrogenic activity is mainly attributed to the presence of the phenolic moiety in intermediates.