Julia Martín

Occurrence of pharmaceutical compounds in wastewater and sludge from wastewater treatment plants: Removal and ecotoxicological impact of wastewater discharges and sludge disposal

The occurrence of sixteen pharmaceutically active compounds in influent and effluent wastewater and in primary, secondary and digested sludge in one-year period has been evaluated. Solid-water partition coefficients (Kd) were calculated to evaluate the efficiency of removal of these compounds from wastewater by sorption onto sludge. The ecotoxicological risk to aquatic and terrestrial ecosystems, due to wastewater discharges to the receiving streams and to the application of digested sludge as fertilizer onto soils, was also evaluated. Twelve of the pharmaceuticals were detected in wastewater at mean concentrations from 0.1 to 32 μg/L. All the compounds found in wastewater were also found in sewage sludge, except diclofenac, at mean concentrations from 8.1 to 2206 μg/kg dm. Ibuprofen, salicylic acid, gemfibrozil and caffeine were the compounds at the highest concentrations. LogKd values were between 1.17 (naproxen) and 3.48 (carbamazepine). The highest ecotoxicological risk in effluent wastewater and digested sludge is due to ibuprofen (risk quotient (RQ): 3.2 and 4.4, respectively), 17α-ethinylestradiol (RQ: 12 and 22, respectively) and 17β-estradiol (RQ: 12 and 359, respectively). Ecotoxicological risk after wastewater discharge and sludge disposal is limited to the presence of 17β-estradiol in digested-sludge amended soil (RQ: 2.7).

Multi‐residue method for the analysis of pharmaceutical compounds in sewage sludge, compost and sediments by sonication‐assisted extraction and LC determination

A method for the simultaneous determination of 16 pharmaceutical compounds in three types of sewage sludge (primary, secondary and anaerobically digested dehydrated sludge), compost and sediment samples is described. Pharmaceutical compounds evaluated were nonsteroidal anti-inflammatory drugs (acetaminophen, diclofenac, ibuprofen, ketoprofen, naproxen and salicylic acid), antibiotics (sulfamethoxazole and trimethoprim), an anti-epileptic drug (carbamazepine), a beta-blocker (propranolol), a nervous stimulant (caffeine), estrogens (17alpha-ethinylestradiol, 17beta-estradiol, estriol and estrone) and lipid regulators (clofibric acid, metabolite of clofibrate and gemfibrozil). The method is based on the ultrasonic-assisted extraction, clean-up by SPE and analytical determination by HPLC with diode array and fluorescence detectors. The best extraction recoveries were achieved in a three-step extraction procedure with methanol and acetone as extraction solvents. Extraction recoveries of several pharmaceutical compounds as caffeine were highly dependent on the type of sample evaluated. The applicability of the method was tested by analyzing primary, secondary and anaerobically digested dehydrated sludge, compost and sediment samples from Seville (Southern Spain). Ten of the sixteen pharmaceutical compounds were detected in sludge samples and five in compost and sediment samples. The highest concentration levels were recorded for ibuprofen in sewage samples, whereas salicylic acid and 17alpha-ethinylestradiol were detected in all of the samples analyzed.

Occurrence, temporal evolution and risk assessment of pharmaceutically active compounds in Donana Park (Spain)

Doñana National Park (Southern Spain) is one of the most emblematic protected areas in Europe and is included in UNESCOs World Heritage List. A 1-year monitoring study was carried out to investigate the presence of 16 pharmaceutical compounds belonging to seven therapeutic groups in wastewater discharges, rivers and streams affecting Doñana Park. Fourteen pharmaceuticals were detected in effluent wastewater at concentration levels up to 26.8 μg L(-1) and thirteen were detected in surface water at concentration levels up to 4.55 μg L(-1). Ibuprofen was the compound at the highest concentration levels. An increase of the concentration levels in surface water was observed in summer months due to the reduction of the flow rates of the rivers. Nevertheless, risk quotient values estimated in surface water were lower than one so no toxicological effect is suspected to occur. The highest average risk quotients were obtained for ibuprofen (risk quotient 0.67±0.28), gemfibrozil (risk quotient 0.52±0.33), propranolol (0.13±0.06) and naproxen (0.10±0.09). Nevertheless, in summer months, risk quotient values up to 9.3 and 10.7 were estimated for the estrogenic compounds 17α-ethinylestradiol and 17β-estradiol.

Simultaneous determination of a selected group of cytostatic drugs in water using high‐performance liquid chromatography–triple‐quadrupole mass spectrometry

In recent years, an increasing concern has risen about the presence of pharmaceuticals in the aquatic environment. Despite their toxicity, increasing consumption and release into the municipal sewage, only a few studies have been focused on cytostatic drugs, mainly due to the lack of methods for their simultaneous analysis. In this work, a method, based on solid-phase extraction prior to high-performance liquid chromatography-triple quadrupole mass spectrometry determination, was optimized and validated for the simultaneous determination of some (14) of the most widely used cytostatic drugs in river water, influent and effluent wastewater. Process efficiency was in the range between 41 and 99% in real samples, except for cytarabine (24%), docetaxel (17%) and methotrexate (30%), due to suppression effects; precision values were <11%, except for gemcitabine (up to 19%); and detection limits were in the range between 0.1 and 38 ng/L. Cytarabine, doxorubicin, etoposide, gemcitabine, iphosphamide and vinorelbine were found at concentration levels up to 14 ng/L in influent and effluent wastewater, showing an insignificant decrease during sewage treatment; cytarabine and gemcitabine were found in effluent wastewater and were also detected in river water associated with effluent discharges.

An affordable method for the simultaneous determination of the most studied pharmaceutical compounds as wastewater and surface water pollutants

There is still an increasing need of knowledge about the presence of pharmaceuticals in the environment in many countries. To contribute to the improvement of this knowledge it should be useful to get not only more reliable methods, but also analytical methods that do not require expensive equipment and, consequently, could be used even in the less developed areas. In the present work, a novel analytical method for the simultaneous determination of several priority pharmaceuticals, as aquatic media pollutants, in wastewater and surface water is reported. The method involves sample treatment by SPE, followed by LC with diode array and fluorescence detection. Parameters that affect the efficiency of the SPE step such as elution solvents, sample pH and cartridge sorbents were evaluated and optimized. The best results were obtained using acetone as elution solvent, acidifying samples to pH 2 and employing Oasis HLB as SPE sorbent. Recoveries of the pharmaceuticals from influent and effluent wastewater and surface water samples were in the range from 61.4 to 123%. LODs were in the range of 0.001-0.323 microg/L and LOQs were between 0.020 and 1.078 microg/L.

Pharmaceutically active compounds in sludge stabilization treatments: anaerobic and aerobic digestion, wastewater stabilization ponds and composting.

Sewage sludge disposal onto lands has been stabilized previously but still many pollutants are not efficiently removed. Special interest has been focused on pharmaceutical compounds due to their potential ecotoxicological effects. Nowadays, there is scarce information about their occurrence in different sludge stabilization treatments. In this work, the occurrence of twenty-two pharmaceutically active compounds has been studied in sludge from four sludge stabilization treatments: anaerobic digestion, aerobic digestion, composting and lagooning. The types of sludge evaluated were primary, secondary, anaerobically-digested and dehydrated, composted, mixed, aerobically-digested and dehydrated and lagoon sludge. Nineteen of the twenty-two pharmaceutically active compounds monitored were detected in sewage sludge. The most contaminated samples were primary sludge, secondary sludge and mixed sludge (the average concentrations of studied compounds in these sludges were 179, 310 and 142 μg/kg dm, respectively) while the mean concentrations found in the other types of sewage sludge were 70 μg/kg dm (aerobically-digested sludge), 63 μg/kg dm (lagoon sludge), 12 μg/kg dm (composted sludge) and 8 μg/kg dm (anaerobically-digested sludge). The antibiotics ciprofloxacin and norfloxacin were found at the highest concentration levels in most of the analyzed sludge samples (up to 2660 and 4328 μg/kg dm, respectively). Anaerobic-digestion treatment reduced more considerably the concentration of most of the studied compounds than aerobic-digestion (especially in the case of bezafibrate and fluoroquinolones) and more than anaerobic stabilization ponds (in the case of acetaminophen, atenolol, bezafibrate, carbamazepine, 17α-ethinylestradiol, naproxen and salicylic acid). Ecotoxicological risk assessment, of sludge application onto soils, has also been evaluated. Risk quotients, expressed as the ratio between the predicted environmental concentration and the predicted non-effect concentration, were lower than 1 for all the pharmaceutically active compounds so no significant risks are expected to occur due to the application of sewage sludge onto soils, except for 17α-ethinylestradiol when chronic toxicity was considered.

Effectiveness of Conventional and Low-Cost Wastewater Treatments in the Removal of Pharmaceutically Active Compounds

In the present work, the effectiveness of conventional wastewater treatments (activated sludge and oxidation ditches) and low-cost wastewater treatments (trickling filter beds, anaerobic lagooning and constructed wetlands) in the removal of pharmaceutically active compounds has been studied. To evaluate the efficiency of removal, 16 pharmaceutically active compounds belonging to seven therapeutic groups (anti-inflammatory drugs, antibiotics, antiepileptic drugs, β-blockers, nervous stimulants, estrogens and lipid regulators) have been monitored during 1-year period in influent and effluent wastewater from 11 wastewater treatment plants of Spain. Mean removal rates of pharmaceutically active compounds achieved in conventional wastewater treatments were slightly higher than those achieved in low-cost treatments, being 64% and 55%, respectively. Ibuprofen, naproxen, salicylic acid and caffeine were the pharmaceutical compounds most efficiently removed, regardless the wastewater treatment applied, with removal rates up to 99%. Anaerobic lagooning was the less effective treatment for the removal of the most persistent compounds: carbamazepine and propranolol.

Occurrence and risk assessment of nonylphenol and nonylphenol ethoxylates in sewage sludge from different conventional treatment processes

In the present work, the concentrations of the organic pollutants nonylphenol (NP) and nonylphenol mono- and diethoxylates (NP1EO and NP2EO, respectively) in primary, secondary, mixed, aerobically-digested, anaerobically-digested, dehydrated, compost and lagoon sludge samples from different sludge treatments have been evaluated. Toxicological risk assessment of these compounds in sludge and sludge-amended soil has also been reported. NP, NP1EO and NP2EO were monitored in sludge samples obtained from treatment plants located in Andalusia (south of Spain) based on anaerobic treatments (11 anaerobic-digestion wastewater treatment plants and 3 anaerobic wastewater stabilization ponds) or on aerobic treatments (3 aerobic-digestion wastewater treatment plants, 1 dehydration treatment plant and 2 composting plants). The sum of NP, NP1EO and NP2EO (NPE) concentrations has been evaluated in relation to the limit value of 50 mg/kg set by the European Union Sludge Directive draft published in April 2000 (Working Document on Sludge). In most of the samples, NP was present at higher concentration levels (mean value 88.0 mg/kg dm) than NP1EO (mean value 33.8 mg/kg dm) and NP2EO (mean value 14.0 mg/kg dm). The most contaminated samples were compost, anaerobically-digested sludge, lagoon sludge and aerobically-digested sludge samples, which contained NPE concentrations in the ranges 44-962 mg/kg dm, 8-669 mg/kg dm, 27-319 mg/kg dm and 61-282 mg/kg dm, respectively. Risk quotients, expressed as the ratios between environmental concentrations and the predicted no-effect concentrations, were higher than 1 for NP, NP1EO and NP2EO in the 99%, 92% and 36% of the studied samples, respectively; and higher than 1 in the 86%, 6% and 2%, respectively, after sludge application to soil, leading to a significant ecotoxicological risk mainly due to the presence of NP.

Behaviour and fluxes of natural radionuclides in the production process of a phosphoric acid plant

In recent years there has been an increasing awareness of the occupational and public hazards of the radiological impact of non-nuclear industries which process materials containing naturally occurring radionuclides. These include the industries devoted to the production of phosphoric acid by treating sedimentary phosphate rocks enriched in radionuclides from the uranium series. With the aim of evaluating the radiological impact of a phosphoric acid factory located in the south-western Spain, the distribution and levels of radionuclides in the materials involved in its production process have been analysed. In this way, it is possible to asses the flows of radionuclides at each step and to locate those points where a possible radionuclide accumulation could be produced. A set of samples collected along the whole production process were analysed to determine their radionuclide content by both alpha-particle and gamma spectrometry techniques. The radionuclide fractionation steps and enrichment sources have been located, allowing the establishment of their mass (activity) balances per year.

Comparison of different extraction methods for the determination of statin drugs in wastewater and river water by HPLC/Q-TOF-MS.

Three preconcentration techniques including solid phase extraction (SPE), dispersive liquid-liquid microextraction (DLLME) and stir-bar sorptive extraction (SBSE) have been optimized and compared for the analysis of six hypolipidaemic statin drugs (atorvastatin, fluvastatin, lovastatin, pravastatin, rosuvastatin and simvastatin) in wastewater and river water samples by high performance liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (HPLC/Q-TOF-MS). Parameters that affect the efficiency of the different extraction methods such as solid phase material, sample pH and elution solvent in the case of SPE; the type and volume of the extracting and dispersive solvent, pH of sample, salt addition and number of extraction steps in the case of DLLME; and the stirring time, pH of sample, sample volume and salt addition for SBSE were evaluated. SPE allowed the best recoveries for most of the analytes. Pravastatin was poorly extracted by DLLME and could not be determined. SBSE was only applicable for lovastatin and simvastatin. However, despite the limitations of having poorer recovery than SPE, DLLME and SBSE offered some advantages because they are simple, require low organic solvent volumes and present low matrix effects. DLLME required less time of analysis, and for SBSE the stir-bar was re-usable. SPE, DLLME and SBSE provided method detection limits in the range of 0.04-11.2 ng L(-1), 0.10-17.0 ng L(-1) for 0.52-2.00 ng L(-1), respectively, in real samples. To investigate and compare their applicability, SPE, DLLME and SBSE procedures were applied to the detection of statin drugs in effluent wastewater and river samples.