Comparison of different types of landfill leachate treatments by employment of nontarget screening to identify residual refractory organics and principal component analysis.

Three different chemical oxidation processes were investigated in terms of their capability to degrade organic chemical components of real mature landfill-leachate in combination with biological treatment run in a Sequencing Batch Biofilter Granular Reactor (SBBGR). H2O2, H2O2 + UV and O3 were integrated with SBBGR and respective effluents were analyzed and compared with the effluent obtained from biological SBBGR treatment alone. In agreement with their respective oxidative power, conventional bulk parameters (residual COD, TOC, Ntot, TSS) determined from the resulting effluents evidenced the following efficacy ranking for degradation: SBBGR/O3 > SBBGR/UV + H2O2 > SBBGR/H2O2 > SBBGR. A more detailed characterization of the organic compounds was subsequently carried out for the four treated streams. For this, effluents were first subjected to a sample preparation step, allowing for a classification in terms of acidic, basic, strongly acidic and strongly basic compounds, and finally to analysis by liquid chromatography/high resolution mass spectrometry (LC/HR-MS). This classification, combined with further data post-processing (non-target screening, Venn Diagram, tri-dimensional plot and Principal Component Analysis), evidenced that the SBBGR/H2O2 process is comparable to the pure biological oxidation. In contrast, SBBGR/O3 and SBBGR/UV + H2O2 not only resulted in a very different residual composition as compared to SBBGR and SBBGR/H2O2, but also differ significantly from each other. In fact, and despite of the SBBGR/O3 being the most efficient process, this treatment remained chemically more similar to SBBGR/H2O2 than to SBBGR/UV + H2O2. This finding may be attributable to different mechanism of degradation involved with the use of UV radiation. Apart from these treatment differences, a series of recalcitrant compounds was determined in all of the four treatments and partly identified as hetero-poly-aromatic species (humic acids-like species).

Simultaneous quantification of neutral and acidic pharmaceuticals and pesticides at the low-ng/l level in surface and waste water.

A new analytical method is presented that allows simultaneous determination of neutral and acidic pharmaceuticals and pesticides in natural waters. The compounds investigated include frequently used pharmaceuticals, i.e., the anti-epileptic carbamazepine, four analgesic/anti-flammatory drugs (ibuprofen, diclofenac, ketoprofen and naproxen) and the lipid regulator clofibric acid and important pesticides including triazines, acetamides and phenoxy acids. Sample enrichment was achieved in one step with a newly developed solid-phase extraction procedure using the Waters Oasis HLB sorbent. The neutral compounds were analyzed by GC-MS in a first step, and then the acidic compounds after derivatization with diazomethane. Relative recoveries using isotope labeled internal standards were between 71 and 118% and the detection limits were in the range of 1 to 10 ng/l in drinking water, surface water and waste water treatment plant effluents (precision: 1-15%). The developed analytical method proved to be very durable during a 3-month field study and the target analytes were detected in concentrations of 5-3,500 ng/l in waste water treatment plant effluents, river water and lake water.