Screening of pharmaceuticals and hormones at the regional scale, in surface and groundwaters intended to human consumption

As part of a regional screening to evaluate the risk, for the health of populations, to certain classes of emerging substances, several families of pharmaceuticals and hormones were looked for in waters intended to drinking. Thus, 52 substances were investigated in 71 surface waters and 70 groundwaters. Results indicate that no water was free of pollutants, regardless of its origin (surface or groundwater) and the season of collect. The pharmaceuticals most frequently detected and with the highest concentration levels were salicylic acid, carbamazepine and acetaminophen. Among hormones, testosterone, androstenedione and progesterone were detected in almost all the samples. Globally the groundwaters were less contaminated than surface waters in regards pharmaceuticals frequencies and levels. On the other side, androgens and progestagens were present with comparable frequencies and levels in both compartments. The risk linked to the presence of these substances on human health is discussed.     

Seasonal variation of organochlorine contaminants in bonito (Sarda sarda L. 1758) and anchovy (Engraulis encrasicolus L. 1758) in Black Sea region, Turkey

The concentrations of indicator polychlorinated biphenyls (PCBs) and organochlorine insecticides were determined in bonito (Sardasarda L. 1758) and anchovy (Engraulisencrasicolus L. 1758) from the Black Sea, Turkey. Concentrations of total indicator PCBs ranged between <1-17.0 in bonito, and <1-17.5 ng/g fresh weight in anchovy, and total of 1,1,1-trichloro-2,2-bis-chlorophenyl-ethane and its metabolites’ (DDTs) concentrations ranged between 13.4-26.3, and 2.96-19.0 ng/g fresh weight in bonito and anchovy respectively. PCB 52, p,p′-DDE and endosulfan (α + β) were found dominant in both of the fish species. Except endosulfan, and some DDT metabolites, none of the studied organochlorine pesticides was detected in the fish samples. Concentrations of PCBs in anchovy were found higher than those in bonito, whereas DDT and endosulfan concentrations were found similar in both of the fish species. All of the fish samples had residue concentrations below the maximum residue limits (MRL) recommended by FAO/WHO Codex Alimentarius Commission.     

Development of a fast instrumental method for the analysis of pharmaceuticals in environmental and wastewaters based on ultra high performance liquid chromatography (UHPLC)-tandem mass spectrometry (MS/MS)

This work describes the development, optimization and validation of an analytical method for the simultaneous detection and identification of 74 pharmaceutically active compounds (PhACs), from various therapeutic groups, in both environmental (ground and surface water) and wastewaters (WW). The method is based on the simultaneous extraction of all target compounds by solid phase extraction (SPE), using a hydrophilic-lipophilic balanced polymer followed by ultra high performance liquid chromatography (UHPLC) tandem mass spectrometry (MS/MS). Two selected reaction monitoring (SRM) transitions have been monitored per compound in order to fulfil the EC guidelines, as well as to ensure an accurate identification of target compounds in the samples. Quantification is performed by internal standard approach, applying 24 specific isotopically labeled compounds. The main advantages of the developed method, besides the selectivity and reliability of the results, is its high throughput. All compounds are extracted in a single step and the instrumental analysis lasts 5 min (NI mode) + 8 min (PI mode), allowing fast throughput of samples. The limits of detection range from 0.01 to 50 ng L⁻¹, depending on the matrix, for most of the compounds. Finally, the method developed has been applied to the analysis of pharmaceuticals in the Ebro river basin (NE Spain).     

Determinations of hexabromocyclododecane (HBCD) isomers in channel catfish, crayfish, hen eggs and fish feeds from China by isotopic dilution LC-MS/MS

HBCD is widely used brominated flame retardant, which is increasingly reported in the environment. A new isotopic dilution LC-MS/MS method was developed to determine three HBCD isomers, α-, β- and γ-HBCD in channel catfish, crayfish, hen eggs and fish feeds in this study, and especially for the first time HBCD isomers composition in crayfish, hen eggs and fish feeds. Soxhlet extractor and GPC cleanup were used, some important steps and crucial parameters were modified and intensified compared with other literatures, and LC and MS/MS conditions were optimized. The limits of quantitation values of 0.01, 0.005 and 0.005 ng g⁻¹ wet weight in channel catfish and crayfish were calculated for three HBCD isomers, respectively; so did 0.1, 0.05 and 0.05 ng g⁻¹ wet weight in eggs and 0.2, 0.1, 0.1 ng g⁻¹ wet weight in fish feeds. Recoveries of α-HBCD, β-HBCD and γ-HBCD were ranged between 75% and 105% for these productions at medium and high-level spiked samples, and between 60% and 85% at low-level spiked samples. The established methods were therefore suitable for the determinations of three HBCD isomers in these productions at trace contamination levels. Moreover, thirty commercial channel catfish, crayfish, hen eggs and fish feeds samples collected from local markets, and thirty home-produced hen eggs from private owners in Hubei province of China, were analyzed to determine whether these productions were contaminated by HBCD. Using the established methods, HBCD emerged in 4 of 30 fish feeds and 3 of 30 home-produced eggs, and in low-ng g⁻¹ wet weight.     

Photocatalytic degradation of the fungicide Fenhexamid in aqueous TiO(2) suspensions: identification of intermediates products and reaction pathways

Liquid-chromatography interfaced with time-of-flight mass spectrometry (LC-TOF/MS) was used to separate and characterize the transformation products arising from TiO₂-photocatalytic degradation of the fungicide Fenhexamid (FEX) in aqueous solution under simulated solar irradiation. Prior to identification, irradiated solutions of FEX (10 mg L⁻¹) were concentrated by solid-phase extraction. Assignments of the mass spectra ions were aided by elemental composition calculations, comparison of structural analogues and available literature, and acquired knowledge regarding mass spectrometry of related heterocyclic compounds. The primary transformation intermediates identified were hydroxyl and/or keto-derivatives. Several positional isomers are typically produced as a consequence of the non-selectivity of the OH radical attack. Moreover, products resulted from the cleavage of the amide and NHdichlorophenol bonds were formed. Finally, cyclic - benzo[d]oxazole intermediates are also formed through an intramolecular photocyclization process and cleavage of halogen - carbon bond. In the case of the hydroxy and/or keto-derivatives, the generic fragmentation scheme obtained from the interpretation of the ESI-TOF-MS data cannot be diagnostic to precisely localize the position of the entering substituent on the FEX molecule, and thus to characterize all its possible oxygenated derivatives by assigning a plausible structure with confidence. On the basis of identified products different pathways of photocatalytic degradation of FEX were proposed and discussed.     

Occurrence of veterinary antibiotics in animal wastewater and surface water around farms in Jiangsu Province, China

The objective of this investigation was to obtain a broad profile of veterinary antibiotics residues in animal wastewater and surface water around large-scale livestock and poultry farms in Jiangsu Province of China. Therefore, 53 samples collected from 27 large-scale animal farms in 11 cities and counties of Jiangsu Province in 2009, were monitored for 10 selected veterinary antibiotics using solid phase extraction and high performance liquid chromatography/electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS) techniques. Ten veterinary antibiotics were found in animal wastewaters, eight antibiotics were detected in pond waters, and animal farm-effluents and river water samples were contaminated by nine antibiotics. The most frequently detected antibiotics were sulfamethazine (75%), oxytetracycline (64%), tetracycline (60%), sulfadiazine (55%) and sulfamethoxazole (51%) which were detected with a maximum concentration of 211, 72.9, 10.3, 17.0 and 63.6 μg L⁻¹, respectively. The maximum concentration of 0.55 μg L⁻¹ for cyromazine, 3.67 μg L⁻¹ for chlortetracycline, 0.63 μg L⁻¹ for sulfadoxine, 39.5 μg L⁻¹ for doxycycline and 0.64 μg L⁻¹ for sulfaquinoxaline were determined in the collected samples. In general, the maximum concentration of the selected veterinary antibiotics was detected in animal wastewaters except for chlortetracycline in animal farm-effluents. In addition, residue levels of selected veterinary antibiotics in animal wastewater and surface water around the farms were related to animal species and have a high spatial variation.     

Profiling the spatial concentration of allethrin and piperonyl butoxide using passive sorptive sampling and thermal desorption capillary GC-MS

Spatial concentration distribution of a chemical in an indoor environment is an important factor in the evaluation of chemical nuisances. However, straightforward techniques for the determination of this distribution are not very common and usually limited in their application. Sorptive sampling using polydimethylsiloxane-coated stir bars and the combination of active and diffusive sampling were shown to allow uncomplicated spatial concentration profiling of multiple compounds in an indoor environment. The validity of the approach was demonstrated in the analysis of the spatial concentration distribution of a pyrethroid insecticide in a common bedroom. The relative concentrations of allethrin and piperonyl butoxide were profiled throughout the room upon the application of an insecticide vaporizer.     

Octyl and nonylphenol ethoxylates and carboxylates in wastewater and sediments by liquid chromatography/tandem mass spectrometry

This work presents an LC–MS–MS-based method for the quantitation of nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) in water, sediment, and suspended particulate matter, and three of their carboxylated derivatives in water. The alkylphenol ethoxylates (APEOs) were analyzed using isotope dilution mass spectrometry with [¹³C₆]-labeled analogues, whereas the carboxylated derivatives were determined by external standard quantitation followed by confirmation using standard additions. The method was used to study APEO’s behavior in a wastewater treatment plant (WWTP), where total dissolved NP0-16EO concentration was reduced by approximately 99% from influent (390 μg l⁻¹) to final effluent (4 μg l⁻¹), and total OP0-5EO concentration decreased by 94% from 3.1 to 0.2 μg l⁻¹. In contrast, the carboxylated derivatives were formed during the process with NP0-1EC concentrations increasing from 1.4 to 24 μg l⁻¹. Short-chain APEOs were present in higher proportions in particulate matter, presumably due to greater affinity for solids compared to the long-chain homologues. NP (0.49 μg l⁻¹) and NP0-1EC (4.8 μg l⁻¹) were the only APEO-related compounds detected in a surface water sample from a WWTP-impacted estuary; implying that 90% of the mass was in the form of carboxylated derivatives. Sediment analysis showed nonylphenol to be the single most abundant compound in sediments from the Baltimore Harbor area, where differences in homologue distribution suggested the presence of treated effluent in some of the sites and non-treated sources in the rest.     

Characterization of humic substances of different origin by means of mass spectrometry and neural networks

Mass spectrometry fingerprinting of humic acids extracted from different soils has been carried out using laser desorption/ionization mass spectrometry (LDI-TOF MS). LDI-TOF MS provides characteristic mass spectra fingerprints for the humic acids of different origin. The information given in the fingerprints was evaluated for natural grouping trends in the samples by neural networks computing tools, such as self-organizing feature map (SOFM). This approach is efficient for recognizing patterns in the humic acids samples independently of their characteristic variability; variability characterizing natural products such as humic substances. The use of multi-layer perceptron artificial neural networks gave a successful classification of the samples.     

小体积液液萃取-GC/MS法测定地表水中有机磷农药

采用小体积液液萃取-气相色谱/质谱联用法测定地表水中有机磷农药,以1.2 mL正己烷为萃取剂,磷酸三苯酯为内标,对8种目标化合物的富集倍数达156～436.方法在1.00 μg/L～20.0 μg/L范围内线性良好,8种有机磷农药的检出限均为0.2 μg/L,实际水样平行测定的RSD为2.1%～9.7%,平均加标回收率...