Reviews - Methods - Sampling - Tracer Methods


Review Papers on PPCP Analytical Methods
Citation Notes Abstract
Richardson, S.D. (2012) Environmental Mass Spectrometry: Emerging Contaminants and Current Issues. Analytical Chemistry 84(2), 747-778.
The Biennial Review in An. Chem.  
Vanderford, B.J., Drewes, J.E., Hoppe-Jones, C., Eaton, A., Haghani, A., Guo, Y.C., Snyder, S., Ternes, T., Schleusener, M. and Wood, C., J. (2012), Method summary for PPCPs, Steroids and Phenols; Water Research Foundation, Denver, CO. Supplemental Material for 4167 Tabular summaries of key method data.
Nussbaumer, S., Bonnabry, P., Veuthey, J.-L. and Fleury-Souverain, S. (2011) Analysis of anticancer drugs: A review. Talanta 85(5), 2265-2289. chemotherapeutics In the last decades, the number of patients receiving chemotherapy has considerably increased. Given the toxicity of cytotoxic agents to humans (not only for patients but also for healthcare professionals), the development of reliable analytical methods to analyse these compounds became necessary. From the discovery of new substances to patient administration, all pharmaceutical fields are concerned with the analysis of cytotoxic drugs. In this review, the use of methods to analyse cytotoxic agents in various matrices, such as pharmaceutical formulations and biological and environmental samples, is discussed. Thus, an overview of reported analytical methods for the determination of the most commonly used anticancer drugs is given.


Papers Focusing on PPCP Analysis
Citation Notes Abstract
San Jose Creek WQL, Method 18CD SOP Preferred method from 4167 study This method covers the determination of 13 pharmaceuticals and personal care products (PPCPs)
in wastewater and groundwater. The procedure concentrates samples, removes some
interferences, and then measures analyte concentrations by two separate LC/MS/MS methods.
Vanderford, B.J., Drewes, J.E., Hoppe-Jones, C., Eaton, A., Haghani, A., Guo, Y.C., Snyder, S., Ternes, T., Schleusener, M. and Wood, C., J. (2012) Evaluation of Analytical Methods for EDCs and PPCPs via Interlaboratory Comparison, Water Research Foundation, Denver, CO.

The 4167 round robin study

Includes Individual Compound Reports: 1, 2, 3; Data; 1, 2, 3; Responses: 1, 2, 3

Eaton, A., Powers, T.H., Spatz, J. and Stark, A. (2010) Evaluating Performance and Comparing Results of Three Laboratories Analyzing City of Chicago Water Samples for EDCs and PPCPs, pp. Thur 9-1, AWWA, Chicago, IL.    
Yu, Y. and Wu, L.S. (2011) Comparison of four extraction methods for the analysis of pharmaceuticals in wastewater. Journal of Chromatography A 1218(18), 2483-2489.   As one category of the most urgent emerging pollutants, pharmaceuticals have provoked much public and scientific attention due to widespread contamination in aquatic environment. In this study, two active methods by Oasis HLB and MCX and two passive methods by XAD-16 and XAD-16/7 were evaluated for determining the concentrations of 10 pharmaceuticals (carbamazepine, clofibric acid, diclofenac, gemfibrozil, ibuprofen, ketoprofen, naproxen, paracetomol, terbutaline and triclosan) in reclaimed wastewater. Recoveries of the target pharmaceuticals extracted by MCX were higher than HLB except for diclofenac and ketoprofen. For the passive methods, the addition of polar resin XAD-7 improved the recovery compared with the addition of XAD-16 only. The mean recoveries of the target analytes by XAD-16/7 ranged from 22 to 75.8%. The limit of quantification (LOQ) ranged between 25 and 280 ng/L. In addition, by comparing the accuracy and precision of XAD-16/7 method and MCX method, we further demonstrated that the XAD-16/7 method can be satisfactorily used for the analysis of pharmaceuticals in wastewater samples. We applied the method to some wastewater samples from sewage treatment plant (STP) nearby Riverside, CA to track the concentration change of pharmaceuticals in the treatment processes. The result shown that pharmaceuticals were effective reduced in STP mostly by activated sludge.
Llewellyn, N., Lloyd, P., Jurgens, M.D. and Johnson, A.C. (2011) Determination of cyclophosphamide and ifosfamide in sewage effluent by stable isotope-dilution liquid chromatography-tandem mass spectrometry. Journal of Chromatography A 1218(47), 8519-8528.   A reliable and specific method was developed for the determination of the cytotoxic drugs cyclophosphamide and ifosfamide in sewage effluent. The most successful combination was found to be Strata-X solid-phase extraction followed by Florisil (R) clean-up with analysis by liquid chromatography-tandem mass spectrometry. Quantification by internal standardisation was achieved using custom synthesised d4-cyclophophosphamide. The mass spectrometer was operated in highly selective reaction monitoring (HSRM) mode, which significantly reduced matrix noise and improved sensitivity. Although it suffered from some ionisation suppression, electrospray ionisation (ESI) was found to give an order of magnitude better sensitivity in terms of limit of detection than atmospheric pressure chemical ionisation (APCI). Using final effluent from two different sewage treatment plants, the method was validated following official European guidelines and shown to be a high performance tool for routine analysis at the sub-nanogram per litre level. Depending on the matrix, the limit of detection for cyclophosphamide was between 0.03 ng/L and 0.12 ng/L and for ifosfamide between 0.05 ng/L and 0.09 ng/L. For cyclophosphamide the accuracy and precision, tested at 1.7 ng/L, were 98-109% and <= 13%. CV respectively. For ifosfamide the accuracy and precision, tested at 1.1 ng/L, were 98-113% and <= 15% CV, respectively. Depending on the sample matrix the absolute recovery of the internal standard was between 57% and 70%. The method was tested by analysis of spot samples taken from the final effluent discharges of two sewage treatment plants; the first using a conventional trickling filter treatment process and second employing activated sludge followed by ultra violet treatment. Cyclophosphamide was detected at 0.19 ng/L at the first plant and at the second detected at 3.7 ng/L and 3.5 ng/L, before and after the UV treatment process; ifosfamide was not detectable at either plant.
Tamtam, F., Mercier, F., Eurin, J., Chevreuil, M. and Le Bot, B. (2009) Ultra performance liquid chromatography tandem mass spectrometry performance evaluation for analysis of antibiotics in natural waters. Analytical and Bioanalytical Chemistry 393(6-7), 1709-1718.   An ultra performance liquid chromatography electrospray tandem mass spectrometry (UPLC/MS/MS) method was developed and validated for the determination of 17 antibiotics in natural waters in one single extraction and chromatographic procedure. Gradient separation conditions were optimised for 17 compounds belonging to five different antibiotic groups: quinolones (oxolinic acid, nalidixic acid, pipemidic acid, flumequine), fluoroquinolones (enoxacin, ciprofloxacin, norfloxacin, ofloxacin, enrofloxacin, sarafloxacin, danofloxacin, difloxacin, lomefloxacin), sulphonamides (sulphamethoxazole, sulphamethazine), nitroimidazole (ornidazole) and diaminopyrimidine (trimethoprim). The separation of all compounds, obtained using a 1.7 mu m particle size column (100 mm x 2.1 mm), was achieved within 10 min time. Water samples were adjusted to pH 7 and extracted using Oasis hydrophilic-lipophilic balance (HLB) solid phase extraction cartridges. After elution with methanol and concentration, extracts were injected in a C18 column (Acquity UPLC BEH C18) and detected by tandem mass spectrometry. Average recovery from 100 ng L-1 fortified samples was higher than 70% for most of the compounds, with relative standard deviations below 20%. Performances of the method (recoveries, detection limit, quantification limit and relative standard deviation) and matrix effects were studied, and results obtained showed that method was suitable for routine analysis of antibiotics in surface water. Samples analysis from Seine River (France) confirmed the interest of antibiotic contamination evaluation in that area.
Kovalova, L., McArdell, C.S. and Hollender, J. (2009) Challenge of high polarity and low concentrations in analysis of cytostatics and metabolites in wastewater by hydrophilic interaction chromatography/tandem mass spectrometry. Journal of Chromatography A 1216(7), 1100-1108.   A method for solid phase extraction and HPLC-MS/MS of the cytostatics 5-fluorouracil, cytarabine, and gemcitabine and human metabolites uracil 1-beta-D-arabinofuranoside and 2',2'-difluorodeoxyuridine in wastewater was established. Wastewater samples from a Swiss hospital were analyzed for 5-fluorouracil, gemcitabine and 2',2'-difluorodeoxyuridine. The limits of quantification were 5.0, 0.9, and 9.0 ng/L and the maximum concentrations detected were 27, 38, and 840 ng/L, respectively. Along with the method development, retention mechanisms on the hydrophilic interaction chromatography (HILIC) stationary phase were studied. Both partitioning and adsorption play a role in the retention on the tested sulfoalkylbetaine modified silica HILIC column material. The contribution of these two processes is changing over the 1.6-40% range water in the mobile phase. Although the specific break point is difficult to determine, adsorption becomes more significant as the fraction of water in the mobile phase decreases below approximately 16%
EPA (2007) Method 1694: Pharmaceuticals and Personal Care Products in Water, Soil, Sediment, and Biosolids by HPLC/MS/MS. SPE protocol used by UMass through 2011 EPA Method 1694 determines pharmaceuticals and personal care products (PPCPs) in environmental samples by high performance liquid chromatography combined with tandem mass spectrometry (HPLC/MS/MS) using isotope dilution and internal standard quantitation techniques. This method has been developed for use with aqueous, solid, and biosolids matrices.
EPA (2007) Method 1698: Steroids and Hormones in Water, Soil, Sediment, and Biosolids by HRGC/HRMS.   EPA Method 1698 determines steroids and hormones in environmental samples by isotope dilution and internal standard high resolution gas chromatography combined with high resolution mass spectrometry (HRGC/HRMS). EPA Method 1698 was developed for use with aqueous, solid, and biosolids matrices.
Kasprzyk-Hordern, B., Dinsdale, R.M. and Guwy, A.J. (2008) Multiresidue methods for the analysis of pharmaceuticals, personal care products and illicit drugs in surface water and wastewater by solid-phase extraction and ultra performance liquid chromatography-electrospray tandem mass spectrometry. Analytical and Bioanalytical Chemistry 391(4), 1293-1308. Basis for UMass LC/MS protocol through 2011 The main aim of the presented research is to introduce a new technique, ultra performance liquid chromatography-positive/negative electrospray tandem mass spectrometry (UPLC-ESI/MS/MS), for the development of new simultaneous multiresidue methods (over 50 compounds). These methods were used for the determination of multiple classes of pharmaceuticals (acidic, basic and neutral compounds: analgesic/anti-inflammatory drugs, antibiotics, antiepileptics, beta-adrenoceptor blocking drugs, lipid regulating agents, etc.), personal care products (sunscreen agents, preservatives, disinfectant/antiseptics) and illicit drugs (amphetamine, cocaine and benzoylecgonine) in surface water and wastewater. The usage of the novel UPLC system with a 1.7 mu m particle-packed column allowed for good resolution of analytes with the utilisation of low mobile phase flow rates (0.05-0.07 mL min(-1)) and short retention times (method times of up to 25 min), delivering a fast and cost-effective method. SPE with the usage of Oasis MCX strong cation-exchange mixed-mode polymeric sorbent was chosen for sample clean-up and concentration. The influence of mobile phase composition, matrix-assisted ion suppression in ESI-MS and SPE recovery on the sensitivity of the method was extensively studied. The method limits of quantification were at low nanogram per litre levels and ranged from tenths of ng L-1 to tens of ng L-1 in surface water and from single ng L-1 to a few hundreds of ng L-1 in the case of wastewater. The instrumental and method intraday and interday repeatabilities were on average less than 5%. The method was successfully applied for the determination of pharmaceuticals in the River Taff (South Wales) and a wastewater treatment plant (WWTP Cilfy-nydd). Several pharmaceuticals and personal care products were determined in river water at levels ranging from single ng L-1 to single mu g L-1.
Vanderford, B.J. and Snyder, S.A. (2006) Analysis of pharmaceuticals in water by isotope dilution liquid chromatography/tandem mass spectrometry. Environmental Science & Technology 40(23), 7312-7320. early isotope dilution method A method has been developed for the trace analysis of 15 pharmaceuticals, four metabolites of pharmaceuticals, three potential endocrine disruptors, and one personal care product in various waters. The method employs solid-phase extraction (SPE) and liquid chromatography/tandem mass spectrometry (LC-MS/MS), using electrospray ionization (ESI) in both positive and negative modes. Unlike many previous LC-MS/MS methods, which suffer from matrix suppression, this method uses isotope dilution for each compound to correct for matrix suppression, as well as SPE losses and instrument variability. The method was tested in five matrices, and results indicate that the method is very robust. Matrix spike recoveries for all compounds were between 88 and 106% for wastewater influent, 85 and 108% for wastewater effluent, 72 and 105% for surface water impacted by wastewater, 96 and 113% for surface water, and 91 and 116% for drinking water. The method reporting limits for all compounds were between 0.25 and 1.0 ng/ L, based on 500 mL of sample extracted and a final extract volume of 500 mu L. Occurrence of the compounds in all five matrices is also reported.


Papers Focusing on PPCP Sampling
Citation Notes Abstract





Tracer Sampling and Analysis
Citation Notes Abstract