Environmental Sample Stability for Pharmaceutical Compound Analysis: Handling and Preservation Recommendations.

Efficient and resilient techniques for handling samples are essential for detecting pharmaceutical compounds in the environment. This study explores a method for preserving water samples during transport before quantitative analysis. The study investigates the stability of 17α-ethynylestradiol (EE2), acetaminophen (ACM), oxytetracycline (OTC), sulfamethoxazole (SMX), and trimethoprim (TMP) after preconcentration within solid-phase extraction (SPE) cartridges. Through various experiments involving different holding times and storage temperatures, it was determined that four pharmaceutical compounds remained stable when stored for a month at 4°C and for six months when stored at -18°C in darkness. Storing these compounds in SPE cartridges at -18°C seemed effective in preserving them for extended periods. In addition, ACM, TMP, OTC, EE2, and SMX remained stable for three days at room temperature. These findings establish guidelines for appropriate storage and handling practices of pharmaceutical compounds preconcentrated from aqueous environmental samples using SPE.

Sol-Gel Synthesis of New TiO2 Ball/Activated Carbon Photocatalyst and Its Application for Degradation of Three Hormones: 17α-EthinylEstradiol, Estrone, and ß-Estradiol.

Many approaches have been investigated to eliminate pharmaceuticals in wastewater treatment plants during the last decades. However, a lack of sustainable and efficient solutions exists for the removal of hormones by advanced oxidation processes. The aim of this study was to synthesize and test new photoactive bio composites for the elimination of these molecules in wastewater effluents. The new materials were obtained from the activated carbon (AC) of Arganian spinosa tree nutshells and titanium tetrachloride by the sol gel method. SEM analysis allowed one to confirm the formation of TiO2 particles homogeneously dispersed at the surface of AC with a controlled titanium dioxide mass ratio, a specific TiO2 anatase structure, and a highly specific surface area, evidenced by ATG, XRD, and BET analysis, respectively. The obtained composites were revealed to quantitatively absorb carbamazepine (CBZ), which is used as a referred pharmaceutical, and leading to its total elimination after 40 min under irradiation with the most effective material. TiO2 high content disfavors CBZ adsorption but improves its degradation. In the presence of the composite, three hormones (17α-ethinylestradiol, estrone, and ß-estradiol) are partially adsorbed onto the composite and totally degraded after 60 min under UV light exposure. This study constitutes a promising solution for the efficient treatment of wastewater contaminated by hormones.

Emerging contaminants detected in aquaculture sites in Java, Indonesia.

Pharmaceuticals of emerging concern (acetaminophen (ACM), trimethoprim (TMP), oxytetracycline (OTC), and sulfamethoxazole (SMX)) were detected in water samples from aquaculture environments and nonaquaculture sites in four regions located on the northern coast of Central Java. ACM was the most prevalent pharmaceutical, with a mean concentration ranging from not detected (n.d.) to 5.5 ± 1.9 ngL-1 (Brebes). Among the target antibiotics (TMP, OTC, SMX), OTC was the most ubiquitous, with a mean concentration varying from n.d. to 8.0 ± 3.3 ngL-1. Correlation analysis demonstrated that there was a significant correlation between TMP and SMX concentrations. Based on ecological risk assessment evaluation, the use of OTC requires serious consideration, as it presented high health risks to algae, while ACM, TMP, and SMX posed an insignificant to moderate risk to algae, invertebrates, and fish. The findings obtained from this study highlight OTC as an emerging contaminant of prominent concern. More attention needs to be given to managing and planning for the sustainable management of shrimp farms, particularly in the northern part of Central Java.

Pharmaceuticals in the marine environment: What are the present challenges in their monitoring?

During the last years, there has been a growing interest in the research focused on the pharmaceutical residues in the environment. Those compounds have been recognized as a possible threat to aquatic ecosystems, due to their inherent biological activity and their "pseudo-persistence". Their presence has been relatively few investigated in the marine environment, though it is the last receiver of the continental contamination. Thus, pharmaceuticals monitoring data in marine waters are necessary to assess water quality and to allow enhancing future regulations and management decisions. A review of the current practices and challenges in monitoring strategies of pharmaceuticals in marine matrices (water, sediment and biota) is provided through the analysis of the available recent scientific literature. Key points are highlighted for the different steps of marine waters monitoring as features to consider for the targeted substance selection, the choice of the marine site configuration and sampling strategies to determine spatio-temporal trends of the contamination. Some marine environment specific features, such as the strong dilution occurring, the complex hydrodynamic and local logistical constraints are making this monitoring a very difficult and demanding task. Thus key knowledge gap priorities for future research are identified and discussed. Suitable passive samplers to monitor pharmaceutical seawater levels need further development and harmonization. Non-target analysis approaches would be promising to understand the fate of the targeted molecules and to enhance the list of substances to analyze. The implementation of integrated monitoring through long-term ecotoxicological tests on sensitive marine species at environmental levels would permit to better assess the ecological risk of these compounds for the marine ecosystems.

Sorption of G-agent simulant vapours on human scalp hair.

Human scalp hair is a biological matrix that can trap chemical vapours from explosives (TNT), drugs (THC) and chemical weapons (yperite). The external contamination of human's hair following exposure to organophosphorus (OP) nerve agent was simulated by model compounds: triethyl phosphate (TEP) and diisopropyl fluorophosphate (DFP). In this work were exposed strands of hair to vapours of TEP and DFP (3 and 7 ppmv) to model sorption kinetics. Sorption isotherms were also investigated at several contamination levels (80-3000 mg min.m-3). OP nerve agent simulants were extracted from hair by soaking in DCM. Raw extracts were analysed in GC-MS/MS to quantify each simulant content in hair. Results were fitted by applying isotherm or kinetic equations. The best model was found to be bimodal first-order, suggesting the co-existence of two different mechanisms of sorption. The best equation to describe OP vapours incorporation on hair was Freundlich model. Thus hair can be used as a passive sensor able to trap chemical G-agents and can also offer valuable information regarding both individual contamination and proof of exposure to chemical weapons.

Zebrafish toxicity assessment of the photocatalysis-biodegradation of diclofenac using composites of TiO2 and activated carbon from Argania spinosa tree nutshells and Pseudomonas aeruginosa.

The occurrence and persistence of pharmaceutical products (PPs) in the environment have recently been well-documented and are a major concern for public health. Their incidence in aquatic ecosystems is the result of their direct release without any prior treatment or insufficient wastewater treatment. Therefore, an efficient and safe posttreatment process for removing PPs must be developed. In this study, we focused on the ability of photocatalysis or combined photocatalysis and biodegradation to effectively and safely remove diclofenac (DCF) and its by-products from water. The heterogeneous photocatalysis system was based on bio-sourced activated carbon obtained from Argania spinosa tree nutshells and Degussa P25 titanium dioxide (ACP-TiO2), and biodegradation involved Pseudomonas aeruginosa. Toxicity tests were conducted with zebrafish embryos to evaluate the applicability of the treatment processes. The results showed that photocatalytic treatment with 0.1 mg/L of ACP-TiO2 9% for 7.5 h is sufficient to eliminate DCF (50 mg L-1) and its by-products from water. Low levels of malformation (< 20%) were detected in zebrafish embryos treated with photocatalyzed DCF solutions at 1, 5, and 7 mg L-1 after 4 days of exposure. After 3 h of incubation, P. aeruginosa was found to reduce the toxicity of DCF (10 mg L-1) photocatalyzed for 2 and 4 h. Additional studies should be conducted to elucidate the biodegradation mechanism.

Desorption of sulphur mustard simulants methyl salicylate and 2-chloroethyl ethyl sulphide from contaminated scalp hair after vapour exposure.

Chemical warfare agents have been used to incapacitate, injure or kill people, in a context of war or terrorist attack. It has previously been shown that hair could trap the sulphur mustard simulants methyl salicylate and 2-chloroethyl ethyl sulphide. In order to investigate simulants persistency in hair after intense vapour exposure, their desorption kinetics were studied by using two complementary methods: hair residual content measurement and desorbed vapour monitoring. Results showed that both simulants were detected in air and could be recovered from hair 2 h after the end of exposure. Longer experiments with methyl salicylate showed that it could still be recovered from hair after 24 h. Our data were fitted with several kinetic models and best correlation was obtained with a bimodal first-order equation, suggesting a 2-step desorption kinetics model: initial fast regime followed by a slower desorption. 2-chloroethyl ethyl sulphide was also detected in the immediate environment after hair exposure for 2 h, and hair simulant content decreased by more than 80%. Our results showed that hair ability to release formerly trapped chemical toxics could lead to health hazard. Their persistency however confirmed the potentiality of hair analysis as a tool for chemical exposure assessment.

From the conventional biological wastewater treatment to hybrid processes, the evaluation of organic micropollutant removal: A review.

Because of the recalcitrance of some micropollutants to conventional wastewater treatment systems, the occurrence of organic micropollutants in water has become a worldwide issue, and an increasing environmental concern. Their biodegradation during wastewater treatments could be an interesting and low cost alternative to conventional physical and chemical processes. This paper provides a review of the organic micropollutants removal efficiency from wastewaters. It analyses different biological processes, from conventional ones, to new hybrid ones. Micropollutant removals appear to be compound- and process- dependent, for all investigated processes. The influence of the main physico-chemical parameters is discussed, as well as the removal efficiency of different microorganisms such as bacteria or white rot fungi, and the role of their specific enzymes. Even though some hybrid processes show promising micropollutant removals, further studies are needed to optimize these water treatment processes, in particular in terms of technical and economical competitiveness.

Efficacy of scalp hair decontamination following exposure to vapours of sulphur mustard simulants 2-chloroethyl ethyl sulphide and methyl salicylate.

Chemical warfare agents are an actual threat and victims' decontamination is a main concern when mass exposure occurs. Skin decontamination with current protocols has been widely documented, as well as surface decontamination. However, considering hair ability to trap chemicals in vapour phase, we investigated hair decontamination after exposure to sulphur mustard simulants methyl salicylate and 2-chloroethyl ethyl sulphide. Four decontamination protocols were tested on hair, combining showering and emergency decontamination (use of Fuller's earth or Reactive Skin Decontamination Lotion RSDL®). Both simulants were recovered from hair after treatment, but contents were significantly reduced (42-85% content allowance). Showering alone was the least efficient protocol. Concerning 2-chloroethyl ethyl sulphide, protocols did not display significant differences in decontamination efficacy. For MeS, use of emergency decontaminants significantly increased showering efficacy (10-20% rise), underlining their usefulness before thorough decontamination. Our results highlighted the need to extensively decontaminate hair after chemical exposure. Residual amounts after decontamination are challenging, as their release from hair could lead to health issues.

Distribution and risk assessment of hydrocarbons (aliphatic and PAHs), polychlorinated biphenyls (PCBs), and pesticides in surface sediments from an agricultural river (Durance) and an industrialized urban lagoon (Berre lagoon), France.

The distributions of organic pollutants (like hydrocarbons, polychlorinated biphenyls (PCBs), and pesticides) and the risks on the ecosystem were studied in the Durance River and the Berre lagoon (France). High levels of aliphatic hydrocarbons were observed in all stations (1399 to 11,202 µg kg(-1) dw). The n-alkanes were mainly from terrigenous origin confirmed by the values of different ratios calculated (carbon preference index (CPI), natural n-alkanes ratio (NAR), terrigenous/aquatic ratio (TAR), and ratio of low molecular weight to high molecular weight (LMW/HMW)). Total polycyclic aromatic hydrocarbon (PAH) concentrations in the surface sediments of the Durance River and Berre lagoon are 57-1528 and 512-863 µg kg(-1) dw, respectively. Several ratios between parent polycyclic aromatic hydrocarbons showed that the sources of hydrocarbons in the sediments were generally more pyrolytic than petrogenic. The sum of seven PCB contents ranged from 0.03 to 13.13 µg kg(-1) dw. Higher levels of PCBs were detected in sediments from the northern parts of the Berre lagoon (stations B1 and B3). Total pesticides contents ranged from 0.02 to 7.15 µg kg(-1) dw. Among these compounds, ∑DDE and ∑DDT contents ranged, respectively, from 0.35 to 1.65 and from 0.37 to 1.52 µg kg(-1) dw. However, PAH and PCB levels are not high enough to be a threat to aquatic organisms and human beings. Total PAH levels were below the effects range low (ERL) of 3500 µg kg(-1) dw. For PCBs, only two stations (B1 and B3) are higher than the effect range median (ERM) of 180 µg kg(-1) dw. For endrin (pesticide), the concentrations are between the ERL (0.02 µg kg(-1) dw) and the ERM (45 µg kg(-1) dw).

Hair analysis as a useful procedure for detection of vapour exposure to chemical warfare agents: simulation of sulphur mustard with methyl salicylate.

Chemical warfare agents (CWA) are highly toxic compounds which have been produced to kill or hurt people during conflicts or terrorist attacks. Despite the fact that their use is strictly prohibited according to international convention, populations' exposure still recently occurred. Development of markers of exposure to CWA is necessary to distinguish exposed victims from unexposed ones. We present the first study of hair usage as passive sampler to assess contamination by chemicals in vapour form. This work presents more particularly the hair adsorption capacity for methyl salicylate used as a surrogate of the vesicant sulphur mustard. Chemical vapours toxicity through the respiratory route has historically been defined through Haber's law's concentration-time (Ct) product, and vapour exposure of hair to methyl salicylate was conducted with various times or doses of exposure in the range of incapacitating and lethal Ct products corresponding to sulphur mustard. Following exposure, extraction of methyl salicylate from hair was conducted by simple soaking in dichloromethane. Methyl salicylate could be detected on hair for vapour concentration corresponding to about one fifth of the sulphur mustard concentration that would kill 50% of exposed individuals (LCt50). The amount of methyl salicylate recovered from hair increased with time or dose of exposure. It showed a good correlation with the concentration-time product, suggesting that hair could be used like a passive sampler to assess vapour exposure to chemical compounds. It introduces great perspectives concerning the use of hair as a marker of exposure to CWA.

Source apportionment of sedimentary hydrocarbons in the Segara Anakan Nature Reserve, Indonesia.

The study aimed to determine the spatial distribution of n-alkanes and polycyclic aromatic hydrocarbons (PAHs) in surface sediments of the Segara Anakan nature reserve and their potential origins using gas chromatography-mass spectrometry. Total alkane concentrations ranged from 3755 to 129,027 µg kg(-1), and the concentrations of 16 PAHs ranged from 375 to 29,517 µg kg(-1). The ratios of specific n-alkanes (e.g., CPI(24-34), WaxC(n), and Paq), including a new proposed index, terrestrial-marine discriminant (TMD), as well as the ratios of selected PAHs (e.g., Ant/∑178, Fl/∑202, BaAnt/∑228, and IPyr/∑276), showed that the sources of hydrocarbons in the sediments were generally biogenic, including both terrigenous and marine, with an anthropogenic pyrolytic contribution (petrogenic and biogenic combustion). For the environmental risk assessment, a sediment quality guideline (SQGs) comparison indicated that the station risk levels ranged from low to medium-low, except for R6, which has a greater impact on the ecological risk for marine organisms.

Photolysis of beta-blockers in environmental waters.

Many drugs such as beta-blockers have been shown to occur in aquatic environments. Even if adequate ecotoxicity data are not available, it is of primary importance to get informations about their fate in environmental waters, particularly about their photofate in sewage treatment plant effluents (STP). The main difficulties when studying pharmaceutical photochemical behaviour in environmental waters, are linked to the very low environmentally relevant concentrations (ng L(-1) to microg L(-1)) which can generate problems in terms of analytical sensitivity. Moreover, the complexity of environmental matrices can modify micropollutants degradation kinetics. The photodegradation of beta-blockers has been compared at two concentration levels (10 microg L(-1) and 10 mg L(-1)) and in two different matrices (pure water and STP effluent). It has been shown that the concentration does not influence beta-blockers degradation pathways, thus allowing the identification of degradation compounds using the 10 mg L(-1) solutions. Although environmental waters speed up the degradation process, the same photoproducts were appeared in both matrices. Using LC-MS/MS, hydroxyl radical additions have been identified as an important degradation pathway for especially pindolol, propranolol and timolol, leading to several positional isomers, corresponding to mono-, di- or tri-hydroxylations. Kinetics of appearance/disappearance of these photoproducts have been studied in STP effluents.

Development and optimisation of a single extraction procedure for the LC/MS/MS analysis of two pharmaceutical classes residues in sewage treatment plant.

A unique extraction procedure leading to the separation of 2 different pharmaceutical classes molecules has been developed and optimised by chemometric tools. From only one sampling, this analytical method allows the determination of 21 pharmaceuticals from corticosteroids and beta-blockers classes. Performing the SPE on Oasis MCX (mixed-mode cation exchange), the sequential elution of each pharmaceutical class is achievable, allowing a high purity level of extracts as well as high recovery rates. Performing a unique sample preparation results in an important save of time. The extracts were then analysed by LC/MS/MS, using a Hibar Purospher Star column for beta-blockers and an X-Bridge column for corticosteroids with formate buffer (pH 3.8)/AcN and water/AcN mobile phases, respectively. This work also includes a study of the chromatographic and mass spectrometric parameters in order to increase the analyte signal. The optimised SPE-LC/MS/MS method was then applied to environmental samples from sewage treatment plant (STP). beta-Blockers and corticosteroids were detected, respectively, in concentrations up to 318 ng L(-1) (sotalol) and 174 ng L(-1) (cortisone), in STP influents. Moreover, both pharmaceutical classes have also been detected in STP effluents. As far as we know, this is the first paper reporting the detection of corticosteroids in environmental waters. The developed analytical method can be used in further studies to investigate the environmental contamination by these drugs.

On-line solid-phase extraction with on-support derivatization for high-sensitivity liquid chromatography tandem mass spectrometry of estrogens in influent/effluent of wastewater treatment plants.

A solid-phase extraction coupled to liquid chromatography/tandem mass spectrometry for the determination of estrogens in sewage influent and effluent has been performed. The possibility of preparing estrogen derivatives directly on a solid-phase extraction bed in which the targeted analytes have been previously isolated and pre-concentrated was explored. This method uses an Oasis HLB column (2.1 mm x 20 mm i.d.) for on-line sample cleanup and derivatization support, and a Sunfire C(18) column (150 mm x 2.1 mm i.d.) with a mobile phase consisting of acetonitrile-water-formic acid for separation. After sample introduction, some matrix interferences are removed by washing up SPE column with methanol-water. Phenolic hydroxyl group of estrogens is subsequently derivatized with dansyl chloride. Reaction takes place in the on-line solid-phase extraction column. The excess of reagent and other matrix interferences are then removed by a second washing. Dansylated estrogens are further back eluted and analyzed with HPLC-MS-MS. The optimized on-line protocol is emphasized owing to a low limit of quantification (1 ng L(-1)) is achieved with only around 1 mL of sample and a low sensitive MS instrument. Developed strategy has been demonstrated to be an improvement over existing methods due to its greater sensitivity and the low volume of matrix used and the total analysis time (extraction, derivatization, analysis) is less than 17 min.

Synthesis of zirconia monoliths for chromatographic separations.

The aim of this work is to join the advantages of two different kinds of stationary phases: monolithic columns and zirconia-based supports. On the one hand, silica monolithic columns allow a higher efficiency with a lower back-pressure than traditional packed columns. On the other hand, chromatographic stationary phases based on zirconia have a higher thermal and chemical stability and specific surface properties. Combining these advantages, a zirconia monolith with a macroporous framework could be a real improvement in separation sciences. Two main strategies can be used in order to obtain a zirconia surface on a monolithic skeleton: coating or direct synthesis. The coverage by a zirconia layer of the surface of a silica-based monolith can be performed using the chemical properties of the silanol surface groups. We realized this coverage using zirconium alkoxide and we further grafted n-dodecyl groups using phosphate derivatives. Any loss of efficiency was observed and fast separations have been achieved. The main advance reported in this paper is related to the preparation of zirconia monoliths by a sol-gel process starting from zirconium alkoxide. The synthesis parameters (hydrolysis ratio, porogen type, precursor concentration, drying step, etc.) were defined in order to produce a macroporous zirconia monoliths usable in separation techniques. We produced various homogeneous structures: zirconia rod 2 cm long with a diameter of 2.3 mm, and zirconia monolith inside fused silica capillaries with a 75 microm I.D. These monoliths have a skeleton size of 2 microm and have an average through pore size of 6 microm. Several separations have been reported.