Optimization of antibiotic analysis in water by solid-phase extraction and high performance liquid chromatography-mass spectrometry/mass spectrometry.

This paper describes the development of an optimized method based on solid-phase extraction (SPE) followed by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-MS/MS) for the simultaneous analysis of ten antibiotic compounds including tetracyclines, sulfonamides, macrolides and quinolones. LC-MS/MS sensitivity has been optimized by alterations to both LC and MS operations. Of the two high resolution columns tested, Waters Symmetry C(18) endcapped and Agilent Zorbax Bonus-RP, the latter was found to show better performance in producing sharp peaks and clear separation for most of the target compounds. Optimization of the MS fragmentation collision and cone energy enhanced the peak areas of the target analytes. The recovery of the target compounds from water samples was most efficient on Waters Oasis HLB SPE cartridge, while methanol was shown to be the most suitable solvent for desorbing the compounds from SPE. In addition, acidification of samples prior to SPE was shown to enhance the recovery of the compounds. To ensure a satisfactory recovery, the flow rate through SPE should be maintained at ≤10 mL min(-1). The method was successfully applied to the analysis of antibiotics from environmental water samples, with concentrations being

Colloids as a sink for certain pharmaceuticals in the aquatic environment.

BACKGROUND, AIM, AND SCOPE: The occurrence and fate of pharmaceuticals in the aquatic environment is recognized as one of the emerging issues in environmental chemistry and as a matter of public concern. Existing data tend to focus on the concentrations of pharmaceuticals in the aqueous phase, with limited studies on their concentrations in particulate phase such as sediments. Furthermore, current water quality monitoring does not differentiate between soluble and colloidal phases in water samples, hindering our understanding of the bioavailability and bioaccumulation of pharmaceuticals in aquatic organisms. In this study, an investigation was conducted into the concentrations and phase association (soluble, colloidal, suspended particulate matter or SPM) of selected pharmaceuticals (propranolol, sulfamethoxazole, meberverine, thioridazine, carbamazepine, tamoxifen, indomethacine, diclofenac, and meclofenamic acid) in river water, effluents from sewage treatment works (STW), and groundwater in the UK. MATERIALS AND METHODS: The occurrence and phase association of selected pharmaceuticals propranolol, sulfamethoxazole, meberverine, thioridazine, carbamazepine, tamoxifen, indomethacine, diclofenac, and meclofenamic acid in contrasting aquatic environments (river, sewage effluent, and groundwater) were studied. Colloids were isolated by cross-flow ultrafiltration (CFUF). Water samples were extracted by solid-phase extraction (SPE), while SPM was extracted by microwave. All sample extracts were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring. RESULTS AND DISCUSSION: Five compounds propranolol, sulfamethoxazole, carbamazepine, indomethacine, and diclofenac were detected in all samples, with carbamazepine showing the highest concentrations in all phases. The highest concentrations of these compounds were detected in STW effluents, confirming STW as a key source of these compounds in the aquatic environments. The calculation of partition coefficients of pharmaceuticals between SPM and filtrate (observed partition coefficients, Kobsp, Kobsoc), between SPM and soluble phase (intrinsic partition coefficients, Kintp, Kintoc), and between colloids and soluble phase (Kcoc) showed that intrinsic partition coefficients (Kintp, Kintoc) are between 25% and 96%, and between 18% and 82% higher than relevant observed partition coefficients values, and are much less variable. Secondly, Kcoc values are 3-4 orders of magnitude greater than Kintoc values, indicating that aquatic colloids are substantially more powerful sorbents for accumulating pharmaceuticals than sediments. Furthermore, mass balance calculations of pharmaceutical concentrations demonstrate that between 23% and 70% of propranolol, 17-62% of sulfamethoxazole, 7-58% of carbamazepine, 19-84% of indomethacine, and 9-74% of diclofenac are present in the colloidal phase. CONCLUSIONS: The results provide direct evidence that sorption to colloids provides an important sink for the pharmaceuticals in the aquatic environment. Such strong pharmaceutical/colloid interactions may provide a long-term storage of pharmaceuticals, hence, increasing their persistence while reducing their bioavailability in the environment. RECOMMENDATIONS AND PERSPECTIVES: Pharmaceutical compounds have been detected not only in the aqueous phase but also in suspended particles; it is important, therefore, to have a holistic approach in future environmental fate investigation of pharmaceuticals. For example, more research is needed to assess the storage and long-term record of pharmaceutical residues in aquatic sediments by which benthic organisms will be most affected. Aquatic colloids have been shown to account for the accumulation of major fractions of total pharmaceutical concentrations in the aquatic environment, demonstrating unequivocally the importance of aquatic colloids as a sink for such residues in the aquatic systems. As aquatic colloids are abundant, ubiquitous, and highly powerful sorbents, they are expected to influence the bioavailability and bioaccumulation of such chemicals by aquatic organisms. It is therefore critical for colloids to be incorporated into water quality models for prediction and risk assessment purposes.

Contamination and ecotoxicology risks of polycyclic aromatic hydrocarbons in Shantou coastal waters, China.

Nine locations in Shantou coastal waters were chosen for the study on contamination and ecotoxicology risks posed by polycyclic aromatic hydrocarbons (PAHs). Sediment samples were collected to investigate PAH distribution behaviour, sources and understand their origin, which is fundamental in predicting their subsequent behaviour. Many approaches and methods were applied to accomplish these objectives and study purpose. The results found revealed the critical importance of improving our understanding of PAH equilibrium relationships. The serious environmental and health concern, imposed by the high concentrations of PAHs in the area, were widely discussed. Furthermore, the location of Shantou within the town and vicinity of Guiyu, which is a booming E-waste processing centre in China, might explain the significance of atmospheric transportation source of PAHs and enhance the occurrence of air-water exchange.

Assessment of the interaction between aquatic colloids and pharmaceuticals facilitated by cross-flow ultrafiltration.

Interactions between pharmaceuticals and aquatic colloids are a key process regulating their environmental fate, but poorly understood. A validated cross-flow ultrafiltration (CFUF) system was used to isolate river colloids and to determine the partition of selected pharmaceuticals between colloidal (>1 kDa but <0.7 microm) and dissolved phases (<1 kDa) by liquid chromatography-tandem mass spectrometry (LC-MS-MS). The kinetics of pharmaceutical binding to colloids was rapid, reaching equilibrium within 5 min. The mass balance of chosen pharmaceuticals through CFUF system was satisfactory for propranolol, sulfamethoxazole, meberverine, carbamazepine, indomethacine, diclofenac, and meclofenamic acid. The partition coefficient normalized to colloidal organic carbon content (Kcoc) varied from 5.45 x 10(4) to 7.54 x 10(5) mL/g for the chosen pharmaceuticals, which are greater than those for endocrine disrupting chemicals (EDCs), suggesting substantially stronger colloidal interactions with pharmaceuticals than with EDCs. Linear relationships were demonstrated between log-Kcoc, and pharmaceutical properties such as log Kow (octanol-water partition coefficient), highlighting the importance of compound hydrophobicity in controlling their binding with colloids. Such a finding is in contrast to that for EDCs whose Kcoc values were independent of their Kow values. The CFUF-LCMS technique has the potential to become a widely applicable tool for quantifying the distribution of emerging organic pollutants between nanoparticles and the dissolved phase.

Contamination of soil, leaves and vegetables by polychlorinated biphenyls in Xiamen region, China.

The paper aimed to identify the primary of polychlorinated biphenyls(PCBs) in the Jiulong River Estuary, investigate the spatial distribution of PCBs contamination in the environment, localize the atmospheric source and evaluate ongoing PCBs emissions by analyzing soil samples collected along the Jiulong River region. In addition, the accumulation of PCBs in the human food chain was quantified by analyzing leaf of orange trees and vegetable samples collected along a gradient of soil/atmospheric contamination moving away from the source. Consequently, the impact on the human health and the ecosystem was quantified, different management options were proposed to reduce this impact and to carry out research on organic contaminants along the Jiulong River and Xiamen region.

The distribution characteristics of bacterial beta-glucosidase activity in Taiwan strait.

Twenty stations were established in the near-shore regions of South Fujian Shoal (116 degrees 10'-119 degrees 00' E, 21 degrees 20'-24 degrees 10' N) on summer and winter cruises during the period from August 1997 and February to March 1998. The distribution pattern of marine bacterial beta-glucosidase activity (beta-GlcA) has been investigated by using fluorogenic model substrate (FMS) technique in order to have better understanding of the beta-GlcA, as well as its relation to marine bacterial biomass, productivity and environmental factors in Taiwan strait. The results showed that: (1) In summer, the average of beta-GlcA at the Southern stations of Taiwan strait was 1.94 nmol/l h. While in winter, the average of beta-GlcA at the Northern stations was 0.86 nmol/l h and the range of variation (0.34-1.89 nmol/l h) was much more narrow than that in summer (0.31-8.1 nmol/l h). (2) According to the carbon conversion factor, the beta-GlcA was 0.14 and 0.062 ugc/l h in summer and winter respectively. These beta-GlcA values were higher than the bacterial production of the two seasons respectively. (3) The beta-GlcA gradually rises from offshore water to near-shore water. (4) The correlation between the beta-GlcA and the bacterial secondary production was not so obvious. (5) The correlation between the section distributions, daily varying of the beta-GlcA and the bacterial production was not obvious. (6) In the surface water, the distribution character of free-state beta-GlcA from bacteria was equal to that of the total beta-GlcA in the whole sea area.