Table 2.
Relevant information related to preconcentration steps and analysis of environmental water samples for diclofenac, E2, and EE2 determination. Costs listed refer to the different analytical options, without considering those related to instrument investment or the possibility, for each method, to be capable of determining several compounds simultaneously (multiresidual analysis). In any case, limiting the determination only to a restricted number of target compounds could be considered a too simplistic approach which might not be useful to fully take advantage of the potentialities of the instrumentation nowadays available
| Sample | Preparation steps | Recovery (%) | Analytical technique | LOQ (μg L−1) | Analysis time and difficultya | Analysis costs (€/sample)b | Reference |
|---|---|---|---|---|---|---|---|
| Diclofenac | |||||||
| Wastewater influent and effluent | 1. Filtration 2. SPE preconcentration 3. Derivatization |
100 | GC-MS/MS | 0.05 | +++ | 40–60 | Carballa et al. (2004, 2005, 2007) |
| raw industrial and municipal wastewater, surface, ground, drinking water | 1. Acidification 2. SPE pre-concentration 3. IS addition |
55–116 | LC-ESI-MS/MS | 0.012–0.02 | ++ | 30–50 | Gros et al. (2006a, b, 2009, 2012), Petrović et al. (2014) |
| Wastewater influent and effluent, groundwater | 1. Filtration 2. SPE preconcentration 3. Derivatization |
55–100 | GC-MS | 0.025 | +++ | 40–60 | Ternes (1998, 2001), Ternes et al. (2003) |
| Wastewater influent and effluent, basin water | 1. Acidification 2. IS addition 3. SPE preconcentration |
100 | LC/ESI-MS/MS | >0.03 | ++ | 30–50 | Sacher et al. (2008), Oosterhuis et al. (2013) |
| Wastewater influent and effluent | 1. Acidification 2. IS addition 3. SPE preconcentration |
100 | UHPLC-MS/MS | 0.05–0.14 | ++ | 30–50 | Gracia-Lor et al. (2010, 2011) |
| River water, WWTP effluent | 1. Addition of deuterated standards 2. Acidification 3. SPE preconcentration 4. IS addition |
99 | LC/ESI/MS | 0.02 | ++ | Letzel et al. (2009) | |
| Wastewater influent and effluent | 1. Acidification 2. SPE preconcentration 3. Derivatization |
65–85 | GC/ion trap-MS/MS | 0.12 | +++ | 40–60 | Serrano et al. (2011) |
| River, wastewater influent and effluent | 1. Filtration 2. SPE preconcentration 3. Derivatization |
56–112 | UHPLC-MS/MS | 0.006–0.012 | +++ | 40–60 | Huang et al. (2011) |
| E2 and EE2 | |||||||
| Surface water and wastewater | 1. Filtration (1.5 μm) 2. SDB-XC disk extraction 3. SPE (C18 and NH2) 4. HPLC elution 5. Derivatization |
88–92 | GC/ion trap-MS/MS | 0.1–2.4 | +++ | 40–60 | Belfroid et al. (1999) |
| Wastewater influent and effluent, rivers | 1. Filtration (1.5 μm) 2. SPE preconcentration 3. Addition of IS |
80–92 | LC/ESI-MS/MS | 0.008–0.8 | ++ | 30–50 | Baronti et al. (2000) |
| Wastewater influent and effluent, anaerobic digester influent and effluent | 1. Filtration (1.5 μm) 2. SPE purification/preconcentration 3. Derivatization |
82–84 | GC/ion trap-MS/MS | 1 | +++ | 40–60 | Ternes (1998), Carballa et al. (2004, 2005, 2007) |
| Synthetic, wastewater influent and effluent, surface waters | 1. Filtration (1.5 μm) 2. MeOH and IS addition 3. SPE purification/preconcentration 4. Derivatization |
79–100 | GC/ion trap-MS/MS | 3–20 | +++ | 40–60 | Quintana et al. (2004) |
| Surface water, wastewater influent and effluent | 1. Filtration | 65–105 | LC/LC-MS/MS | 0.002–0.003 | +++ | 20–40 | Gorga et al. (2013) |
a+: low, ++: moderate, +++: high
bAnalysis cost was estimated including the cost of the column (lasting about 500 injections) and SPE cartridge and amortization of instrumentation (lasting 5 years)