Pharmaceuticals, detection

This chapter will review the levels and distribution of pharmaceuticals detected in both waste and river waters from the Ebro river Basin and gives an example about the use of established hazard indexes to estimate the possible risks posed by the pharmaceutical levels detected towards different aquatic organisms (algae, daphnia, and fish). Results presented in this chapter were integrated in the FP6 European Union project AQUATERRA (contract no. 505428). 

On this context, it is important to set up analytical methods and monitoring programs in order to characterize what are the pharmaceuticals detected in... 

Fig. 2 Levels of pharmaceuticals detected in wastewater influent (a) and effluent (b), where n means the total number of samples analyzed to what concentrations indicated refer to...

Table 3 Total loads (expressed as gram per day per 1,000 inhabitants) of pharmaceuticals detected in WWTP effluents that are afterwards discharged into receiving river waters. Loads are expressed as the range of the amounts detected in each sampling period altogether with average and mean values...

Fig. 6 Concentrations (ng L ) of some of the most ubiquitous pharmaceuticals detected in (a) wastewater effluents and (b) river water downstream of three WWTP in the Ebro river basin in relationship to the dilution factor...

Fig. 7 Comparison between mean monthly flow (m3 s ) with the sum of all concentrations levels of the pharmaceuticals detected in (a) Arga river the tributary receiving the discharge of WWTP4, and (b) Ebro river in Zaragoza, which receives the discharge of WWTP5...

Table 4 EC50 (in mg L ) used to calculate PNEC (by dividing EC50 by an assessment factor (AF) of 1,000), for fish, daphnids (Daphnia magna) and algae for some of the most ubiquitous pharmaceuticals detected in environmental waters...

Fig. 10 Influence of hydraulic retention time (HRT) in pharmaceutical removal. The most ubiquitous pharmaceuticals detected are shown...

Kim I, Yamashita N, Tanaka H (2009) Performance of UV and UV/H2O2 processes for the removal of pharmaceuticals detected in secondary effluent of a sewage treatment plant in Japan. J Hazard Mater 166 1134-1140... 

Valtrate or standard pharmaceuticals Detection Hydrochloric acid-acetic acid reagent No. 17... 

TABLE 10.4 Pharmaceutical Mass Recovered in POCIS and Estimated Aqueous Concentrations of Pharmaceuticals Detected in Passive Samplers Upstream and Downstream of WWTP Discharges and in WWTP EfDuent"... 

The fermentation-derived food-grade product is sold in 50, 80, and 88% concentrations the other grades are available in 50 and 88% concentrations. The food-grade product meets the Vood Chemicals Codex III and the pharmaceutical grade meets the FCC and the United States Pharmacopoeia XK specifications (7). Other lactic acid derivatives such as salts and esters are also available in weU-estabhshed product specifications. Standard analytical methods such as titration and Hquid chromatography can be used to determine lactic acid, and other gravimetric and specific tests are used to detect impurities for the product specifications. A standard titration method neutralizes the acid with sodium hydroxide and then back-titrates the acid. An older standard quantitative method for determination of lactic acid was based on oxidation by potassium permanganate to acetaldehyde, which is absorbed in sodium bisulfite and titrated iodometricaHy. 

Other appHcations of firefly hioluminescence include measurement of the activity of bacteria in secondary sewage treatment activated sludge (296,297), detection of bacteria in clean rooms and operating rooms, measurement of bacteria in bottled foods, beverages (298), and pharmaceuticals (299), determination of the antimicrobial activity of potential dmgs (300), determination of the viabiHty of seeds (301), and measuring marine biomass concentrations as a function of ocean depth or geographical location (302). 

Quantitative mass spectrometry, also used for pharmaceutical appHcations, involves the use of isotopicaHy labeled internal standards for method calibration and the calculation of percent recoveries (9). Maximum sensitivity is obtained when the mass spectrometer is set to monitor only a few ions, which are characteristic of the target compounds to be quantified, a procedure known as the selected ion monitoring mode (sim). When chlorinated species are to be detected, then two ions from the isotopic envelope can be monitored, and confirmation of the target compound can be based not only on the gc retention time and the mass, but on the ratio of the two ion abundances being close to the theoretically expected value. The spectrometer cycles through the ions in the shortest possible time. This avoids compromising the chromatographic resolution of the gc, because even after extraction the sample contains many compounds in addition to the analyte. To increase sensitivity, some methods use sample concentration techniques. 

Chiral separations have become of significant importance because the optical isomer of an active component can be considered an impurity. Optical isomers can have potentially different therapeutic or toxicological activities. The pharmaceutical Hterature is trying to address the issues pertaining to these compounds (155). Frequendy separations can be accompHshed by glc, hplc, or ce. For example, separation of R(+) and 5 (—) pindolol was accompHshed on a reversed-phase ceUulose-based chiral column with duorescence emission (156). The limits of detection were 1.2 ng/mL of R(+) and 4.3 ng/mL of 3 (—) pindolol in semm, and 21 and 76 ng/mL in urine, respectively. 

Gas Chromatography Analysis. From a sensitivity standpoint, a comparable technique is a gas chromatographic (gc) technique using flame ioni2ation detection. This method has been used to quantify the trimethylsilyl ester derivative of biotin in agricultural premixes and pharmaceutical injectable preparations at detection limits of approximately 0.3 pg (94,95). 

The NMR chemical shifts of non-aromatic isothiazoles can be predicted with reasonable accuracy using standard substituent increments. A particular usefulness of NMR is its ability to distinguish between very similar compounds, and for this reason NMR finds application in pharmaceutical and other analyses. As an example CNMR allows ready distinction of the dlastereolsomers of dehydromethionine (14) and the possibility of detection of one dlastereolsomer in the presence of the other (79JOC2632). 

This procedure was tested in the analysis of pharmaceutical products Poltava s bishofite (series Elite and Profi ) and a brine of bischofite with rusty precipitate. The data bear out the sufficient accuracy and reproducibility of the proposed procedure which allows to perform the determination magnesium, iron, copper and zinc ions at concentrations above 10 M. It was found that the content of Mg ion in the studied brine decreases in comparison with Poltava s bishofite . The Fe, Cu and Zn ions were not detected in the brine. 

Note Silica gel, kieselguhr and polyamide layers can be used as stationary phases. Not all acids are stained on RP layers. Amino layers yield a pale blue background. The detection limits are in the pg range for carboxylic acids [1], thioglycolic and dithioglycolic acids [2] and for antithyroid pharmaceuticals [4] they are about 5 ng per chromatogram zone for sterols and steryl esters [6]. 

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