Determination of pharmaceuticals in sewage sludge and biochar from hydrothermal carbonization using different quantification approaches and matrix effect studies.

Producing valuable biochar from waste materials using thermal processes like hydrothermal carbonization (HTC) has gained attention in recent years. However, the fate of micropollutants present in these waste sources have been neglected, although they might entail the risk of environmental pollution. Thus, an HPLC-MS/MS method was developed for 12 pharmaceuticals to determine the micropollutant load of biochar, which was made from sewage sludge via HTC within 4 h at 210 °C. Pressurized liquid extraction was applied to extract the compounds. Because of the high load of co-extracted matter, matrix effects in HPLC-MS/MS were investigated using matrix effect profiles. Interfering compounds suppressed 50% of the phenazone signal in sewage sludge and 70% in biochar, for example. The quantification approaches external calibration, internal standard analysis, and standard addition were compared considering recovery rates, standard deviations, and measurement uncertainties. The external analysis resulted in decreased or enhanced recovery rates. Spiking before LC-MS/MS compensated instrumental matrix effects. Still, recovery rates remained below 70% for most compounds because this approach neglects sample losses during the extraction. Internal standards compensated for the matrix effects sufficiently for up to five compounds. The standard addition over the whole procedure proved to compensate for the matrix effects for 11 compounds and achieved recovery rates between 85 and 125%. Additionally, results showed good reproducibility and validity. Only sulfamethoxazole recovery rate remained below 70% in sewage sludge. Real sample analysis showed that three pharmaceuticals were detected in the biochar, while the corresponding sewage sludge source contained 8 of the investigated compounds.

Chemical and toxicological evaluation of transformation products during advanced oxidation processes.

The entry of pharmaceuticals into the water cycle from sewage treatment plants is of growing concern because environmental effects are evident at trace levels. Ozonation, UV- and UV/H(2)O(2)-treatment were tested as an additional step in waste water treatment because they have been proven to be effective in eliminating aqueous organic contaminants. The pharmaceuticals carbamazepine, ciprofloxacin, diclofenac, metoprolol and sulfamethoxazole as well as the personal care products galaxolide and tonalide were investigated in terms of degradation efficiency and by-product formation in consideration of toxic effects. The substances were largely removed from treatment plant effluent by ozonation, UV- and UV/H(2)O(2)-treatment. Transformation products were detected in all tested treatment processes. Accompanying analysis showed no genotoxic, cytotoxic or estrogenic potential for the investigated compounds after oxidative treatment of real waste waters. The results indicate that by-product formation from ozonation and advanced oxidation processes does not have any negative environmental impact.

Removal of APIs and bacteria from hospital wastewater by MBR plus O(3), O(3) + H(2)O(2), PAC or ClO(2).

The objective of this study has been to develop technologies that can reduce the content of active pharmaceutical ingredients (APIs) and bacteria from hospital wastewater. The results from the laboratory- and pilot-scale testings showed that efficient removal of the vast majority of APIs could be achieved by a membrane bioreactor (MBR) followed by ozone, ozone + hydrogen peroxide or powdered activated carbon (PAC). Chlorine dioxide (ClO(2)) was significantly less effective. MBR + PAC (450 mg/l) was the most efficient technology, while the most cost-efficient technology was MBR + ozone (156 mg O(3)/l applied over 20 min). With MBR an efficient removal of Escherichia coli and enterococci was measured, and no antibiotic resistant bacteria were detected in the effluent. With MBR + ozone and MBR + PAC also the measured effluent concentrations of APIs (e.g. ciprofloxacin, sulfamethoxazole and sulfamethizole) were below available predicted no-effect concentrations (PNEC) for the marine environment without dilution. Iodinated contrast media were also reduced significantly (80-99% for iohexol, iopromide and ioversol and 40-99% for amidotrizoateacid). A full-scale MBR treatment plant with ozone at a hospital with 900 beds is estimated to require an investment cost of €1.6 mill. and an operating cost of €1/m(3) of treated water.

Efficiency, costs and benefits of AOPs for removal of pharmaceuticals from the water cycle.

Different advanced oxidation processes (AOP) were developed for the treatment of highly loaded wastewater streams. Optimisation of removal and improvement of efficiency were carried out on a laboratory, semiworks and pilot plant scale. The persistent cytostatic drug cyclophosphamide was selected as a reference substance regarding elimination and evaluation of the various oxidation processes because of its low degradability rate. The investigated processes are cost-efficient and suitable regarding the treatment of wastewater streams since they lead to efficient elimination of antibiotics and antineoplastics. A total reduction of toxicity was proven by means of the umuC-test. However, in order to reduce pharmaceuticals from the water cycle, it must be considered that the input of more than 80 % of the pharmaceuticals entering wastewater treatment systems results from private households. Therefore, advanced technologies should also be installed at wastewater treatment plants.

Evaluation of column bleed by using an ultraviolet and a charged aerosol detector coupled to a high-temperature liquid chromatographic system.

In this study, five different HPLC columns were heated to 200 degrees C using a homemade heating system which can be operated in temperature programmed mode. The column bleed as an indicator of induced degradation of the stationary phase material was evaluated using a charged aerosol detector (CAD) and an ultraviolet diode array detector (UV-DAD) at different wavelengths. The silica based C-18 stationary phase gave the highest bleed, and the carbon clad titanium dioxide column the lowest bleed. This was independent of both the detection technique and the wavelength.

Development and application of a specially designed heating system for temperature-programmed high-performance liquid chromatography using subcritical water as the mobile phase.

A specially designed heating system for temperature-programmed HPLC was developed based on experimental measurements of eluent temperature inside a stainless steel capillary using a very thin thermocouple. The heating system can be operated at temperatures up to 225 degrees C and consists of a preheating, a column heating and a cooling unit. Fast cycle times after a temperature gradient can be realized by an internal silicone oil bath which cools down the preheating and column heating unit. Long-term thermal stability of a polybutadiene-coated zirconium dioxide column has been evaluated using a tubular oven in which the column was placed. The packing material was stable after 50h of operation at 185 degrees C. A mixture containing four steroids was separated at ambient conditions using a mobile phase of 25% acetonitrile:75% deionized water and a mobile phase of pure deionized water at 185 degrees C using the specially designed heating system and the PBD column. Analysis time could be drastically reduced from 17 min at ambient conditions and a flow rate of 1 mL/min to only 1.2 min at 185 degrees C and a flow rate of 5 mL/min. At these extreme conditions, no thermal mismatch was observed and peaks were not distorted, thus underlining the performance of the developed heating system. Temperature programming was performed by separating cytostatic and antibiotic drugs with a temperature gradient using only water as the mobile phase. In contrast to an isocratic elution of this mixture at room temperature, overall analysis time could be reduced two-fold from 20 to 10 min.

Fate and behaviour of diclofenac during hydrothermal carbonization.

Hydrothermal carbonization (HTC) has become an esteemed method to convert sewage sludge into biochar. Besides dewatering and disinfection the process is suggested to reduce the micropollutant load, which would be beneficial for the use of biochar as fertilizer. This study was designed to examine reduction of micropollutants and formation of transformation products during HTC using the example of diclofenac. We investigated compounds' removal at HTC conditions in inert experiments and in real samples. Results showed that HTC temperature (>190 °C) and pressure (∼15 bar) have the potential to fully degrade diclofenac in inert experiments and spiked sewage sludge (>99%) within 1 h. However, interfering effects hinder full removal in native samples resulting in 44% remaining diclofenac. Additionally, a combination of suspected-target and non-target analysis using LC-MS/MS and LC-HRMS resulted in the determination of six transformation products. These products have been reported in biochar from HTC for the first time, although other studies described them for other processes like advanced oxidation. Based on the detected transformation products, we proposed a degradation mechanism reflecting HTC reactions such as dehydroxylation and decarboxylation.

Pharmaceutical load in sewage sludge and biochar produced by hydrothermal carbonization.

We investigated the removal of twelve pharmaceuticals in sewage sludge by hydrothermal carbonization (HTC), which has emerged as a technology for improving the quality of organic waste materials producing a valuable biochar material. In this study, the HTC converted sewage sludge samples to a biochar product within 4h at a temperature of 210 °C and a resulting pressure of about 15 bar. Initial pharmaceutical load of the sewage sludge was investigated as well as the residual concentrations in biochar produced from spiked and eight native sewage sludge samples from three waste water treatment plants. Additionally, the solid contents of source material and product were compared, which showed a considerable increase of the solid content after filtration by HTC. All pharmaceuticals except sulfamethoxazole, which remained below the limit of quantification, frequently occurred in the investigated sewage sludges in the µg/kg dry matter (DM) range. Diclofenac, carbamazepine, metoprolol and propranolol were detected in all sludge samples with a maximum concentration of 800 µg/kgDM for metoprolol. HTC was investigated regarding its contaminant removal efficiency using spiked sewage sludge. Pharmaceutical concentrations were reduced for seven compounds by 39% (metoprolol) to≥97% (carbamazepine). In native biochar samples the four compounds phenazone, carbamazepine, metoprolol and propranolol were detected, which confirmed that the HTC process can reduce the load of micropollutants. In contrast to the other investigated compounds phenazone concentration increased, which was further addressed in thermal behaviour studies including three structurally similar potential precursors.

A strategy for the systematic development of a liquid chromatographic mass spectrometric screening method for polymer electrolyte membrane degradation products using isocratic and gradient phase optimized liquid chromatography.

Within the scope of research for target and non-target LC-MS/MS analysis of membrane degradation products of polymer electrolyte membrane fuel cells, a systematic method development for the separation of structurally similar compounds was performed by phase optimized liquid chromatography. Five different stationary phases with different selectivities were used. Isocratic separation for 4-hydroxybenzoic acid, isophthalic acid, terephthalic acid, 4-hydroxybenzaldehyde and 4-formylbenzoic acid was achieved on a C18 and a Phenyl phase. Using the PRISMA model the separation efficiency was optimized. This was achieved on a serially connected mixed stationary phase composed of 30 mm C18, 150 mm Phenyl and 60 mm C30. For the LC-MS screening of unknown degradation products from polymer electrolyte membranes in the product water of a fuel cell, a solvent gradient is mandatory for less polar or later eluting compounds. By means of 4-mercaptobenzoic acid it could be shown that a solvent gradient can be applied in order to elute later eluting compounds in a short time. The adaptability of this method for the qualitative analysis by target and non-target LC-MS/MS screening has been shown by means of 4-hydroxybenzoic acid. The combination of solvent gradient and isocratic conditions makes this approach attractive for the purpose of a screening method for known and unknown analytes in a water sample.