Pharmaceutical antibiotic compounds in soils - a review - Susane.info

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150 Thiele-Bruhn J. Plant Nutr. Soil Sci. 2003, 166, 145±167 Table 3: Continued. Tabelle 3: Fortsetzung. further details a Reference Sample Extractant Clean-up Column type Eluent Detection & -limits Class/ compound Johannsen, 1991 100 ll, post column derivat.: DMA/H SO 2 4 UV 320 nm; 10 lg kg ±1 MeOH:phosphate buffer (pH 4)(9:1), 0.7 ml min ±1 Hypersil ODS 250”4; 5 lm liquid/liquid MeCl 2 animal feed MeOH/phosphate buffer (pH 4)(9:1) Polyethers (Salinomycin, Monensin, Lasalocid) Asukabe et al., 1994 pre column derivat.: 1-(bromoacetyl) pyrene FLD ex 360 em 420 nm MeOH:H O 97:3, 2 isocratic animal feed ACN SPE: Silica Develosil 5 C18 250”4.6; 100 lm UV 270 nm Samuelsen et al., 1994 0.1 N NaOH centrifugation C18, 100”4.6; 3 lm 0.05 M H PO /ACN, 3 4 gradient marine sediment Sulfonamides UV 280 nm 40 C, 50 ll Ingerslev and Halling-Sùrensen, 2000 ACN:16.7 mM acetic acid/ (pH 5 with 4M NaOH) (17.5:82.5 ), 1mlmin ±1 Phenomenex ODS2 C18 125”4.6; 5lm H O centrifugation, 2 0.45 lm filtration sewage sludge UV 265 nm 22 C, 10 ll Thiele, 2000 0.01 M H PO / 3 4 MeOH, 1 ml min ±1 , gradient soil MeOH SPE: C18 Nucleosil C18 250”4.6; 100±5 lm 25 C, 50 ll Haller et al., 2002 H O:1mM NH OAc+10 % 2 4 ACN/ACN, 0.25 ml min ±1 UV; MS/MS ESI+ , gradient Nucleosil C18 125”3; 100±5 lm pH 9 with KOH, EtOAc separation of EtOAc, 0.45 lm filtration animal manure +Trimethoprim Lindsey et al., 2001 MS ESI+;
J. Plant Nutr. Soil Sci. 2003, 166, 145±167 Antibiotic in soils 151 ionization at atmospheric pressure (APCI) or electrospray ionization (ESI) is used (Oka et al., 1997; Carson et al., 1998). Niessen (1998) reviewed the analysis of antibiotics by LC-MS and stated that this detection method is most sensitive for a multitude of compounds. Numerous applications already exist for LC-MS. Kamel et al. (1999) detected the highest sensitivity for TCs with LC-ESI-MS/MS in the positive ion mode and by addition of 1 % acetic acid in the mobile phase. In comparison, Lindsey et al. (2001) used ammonia formiate/formic acid in combination with a water/ methanol gradient. However, for FQs, fluorescence detection after derivatization and liquid chromatography was superior to LC-MS/MS (Golet et al., 2001). To date, the traditional, semi-quantitative detection of antibiotics by microbial inhibition tests such as agardiffusion and bioautography (Katz and Katz, 1983; Süûmuth et al., 1987) is carried out only to supplement chemical analysis. However, for a complete assessment of antibiotics, not only their quantity, but also their antibiotic potential must be determined. For this purpose, new techniques that combine chemical extraction, chromatographic separation and determination by microbial assays have been developed (e.g. Sczesny et al., 2003). Hestbjerg Hansen et al. (2001) developed a biosensor for the selective detection of bioavailable and bioactive trace residues of TCs in soil. 4 Input and concentrations in the soil environment Soils are a habitat and source of indigenous, antibiotics producing microorganisms (Gottlieb, 1976; Thomashow et al., 1997). Among numerous other soil microorganisms, 30 to 50 % of actinomycetes isolated from soil are able to synthesize antibiotics (Topp, 1981). Such antibiotics, biosynthesized in situ, are found especially in the soil rhizosphere with concentrations of up to 5 lg g ±1 (Soulides, 1965; Lumsden et al., 1992; Shanahan et al., 1992). However, findings of pharmaceutical antibiotics in the environment increase. Like other pharmaceuticals, these compounds are optimized in their pharmacokinetics in such a way that they do not accumulate in the organism. After medication, they are mostly excreted as parent compounds, whereas metabolites might be also bioactive (Bouwman and Reus, 1994; Schadewinkel-Scherkl and Scherkl, 1995; Kümmerer et al., 2000). Excretion rates following the passage throughthegastro-intestinaltractareintherangeof40to90 %for SAs and TCs (Berger et al., 1986; Winckler and Grafe, 2001). Compilations of excretion rates were published by Zuccato et al. (2001), Halling-Sùrensen et al. (2001), and Jjemba (2002). Rates vary among the single antibiotic substances, the treated species and depend on the mode of application, as it was shown for SAadministered to pigs (Haller et al., 2002). 4.1 Anthropogenic input Major portions of antibiotics are excreted after intra-corporal medication or are rinsed from the skin after dermal application. Consequently, antibiotics reach agricultural soils directly through grazing livestock or indirectly through the use of manure and sewage sludge as fertilizer (Jùrgensen and Halling-Sùrensen, 2000). In addition, wastewater and runoff from agricultural land are mainly responsible for the contamination of aquatic systems (Hirsch et al., 1999; Alder et al., 2001). Afurther significant source of antibiotics in the environment is their use in aquaculture for fish production. Here they are directly introduced into surface water (Römbke et al., 1996). Among other compounds, TCs, nitrofurans, and SAs are used mainly for this purpose (Löscher et al., 1994) and result in residual concentrations of several hundred mg kg ±1 in aquatic sediments (Jacobsen and Berglind, 1988; Samuelsen et al., 1992; Coyne et al., 1994). Flooding of shore soils with contaminated surface water may possibly yield an input of antibiotics. In contrast, environmental contamination due to the production and distribution of pharmaceuticals can mostly be excluded. However, severe ground water contamination following the deposition of pharmaceutical wastes from antibiotic production was reported by Holm et al. (1995). Since the 1950s, antibiotics have been used as pesticides, especially oxytetracycline and streptomycin, which are commonly used in fruit, vegetable, and ornamental plant production. In the USA, 0.5 % of the total antibiotic consumption of approximately 10,000 t is from the application to plants (McManus et al., 2002). In the vicinity of animal houses used for pig and poultry breeding, antibiotics were detected in dust from the exhaust air of the stable ventilation (Hamscher et al., 2002b; Thiele-Bruhn et al., 2003a). Intra-corporal degradation processes usually proceed in the faeces (Langhammer, 1989; Loke et al., 2000). In contrast, antibiotics not metabolized in the organism are often found as recalcitrant after excretion (Bouwman and Reus, 1994; Schadewinkel-Scherkl and Scherkl, 1995). Thus, several antibiotic compounds persist in the environment (Gavalchin and Katz, 1994; Kümmerer et al., 2000; Kühne et al., 2000) and are not transformed, e.g. by aeration of manure even at increased ambient temperature (Winckler and Grafe, 2001) or sewage water treatment (Richardson and Bowron, 1985). These substances are likely to reach aquatic sediments through waste water or agricultural soils after fertilization with manure and sewage sludge, respectively. 4.2 Environmental concentrations The discussed sources of pharmaceuticals result in detectable residual concentrations in diverse environmental compartments and even in drinking water (Heberer and Stan, 1998; Hirsch et al., 1999). In the USA, a nationwide survey of pharmaceutical compounds revealed that among numerous other pharmaceuticals, a number of veterinary and human antibiotics were detected in 27 % of 139 river water samples at concentrations of up to 0.7 lg l ±1 (Kolpin et al., 2002). In England, representative single substances from the classes of macrolides, SAs, and TCs were determined in river water in concentrations of ca. 1 lg l ±1 (Watts et al., 1982), a concentration that reduced aqueous microbial activity in biotests (Backhaus and Grimme, 1999). In marine sediment underneath fish farms, residual oxytetracycline concentrations of 500 to 4000 lg kg ±1 were commonly observed and
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Pharmaceutical antibiotic compounds in soils - a review - Susane.info

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