Monika Moeder

Municipal landfill leachates: A significant source for new and emerging pollutants

Landfills have historically remained the most common methods of organized waste disposal and still remain so in many regions of the world. Thus, they may contain wastes resulting from several decades of disposal and decomposition with subsequent release of organic compounds that may have environmental, wildlife and human health consequences. Products containing different types of additives with unique beneficial improvement properties are in daily use. However, when these products are decomposed, additives are release into the environment, some of which have been shown to have negative environmental impacts, resulting in the ban or at least restricted application of some chemicals. New and emerging compounds are continuously discovered in the environment. Herein, we report qualitative and quantitative data on the occurrence of new and emerging compounds with increasing environmental and public health concern in water- and particle phase of landfill leachates. Under normal environmental conditions, several of these chemicals are persistent high-volume products. Identified chemicals in the leachates at nanogram (ng) or microgram (microg) per liter levels include - chlorinated alkylphosphates such as tris(1-chloro-2-propyl) phosphate (TCPP), N-butyl benzensulfonamide (NBBS), the insect repellent diethyl toluamide (DEET) and personal care products such as the non-steroidal anti-inflammatory drug ibuprofen and polycyclic musk compounds. Among new and emerging contaminants, perfluorinated compounds (PFCs) were measured in the water phase at concentrations up to 6231 ng/L. Compared with the other chemicals, PFCs were primarily distributed in water phase. An effective removal method for PFCs and other polar and persistent compounds from landfill leachates has been a major challenge, since commonly used treatment technologies are based on aeration and sedimentation. Thus, the present study has shown that municipal landfill leachates may represent a significant source of concern for legacy, new and emerging chemicals in groundwater.

Solid-phase microextraction-gas chromatography-mass spectrometry of biologically active substances in water samples

A solid-phase microextraction (SPME) method for determining trace amounts of polar, biologically active substances in water systems was developed and compared with solid-phase extraction followed by derivatization and GC-MS. SPME was examined with respect to the simultaneous determination of pharmaceuticals such as ibuprofen, paracetamol, phenazone, carbamazepine, and nonylphenols known to be xenoestrogens. The extraction performance of different SPME fibre coatings was studied. Coatings like polyacrylate and Carbowax-divinylbenzene proved to be the best suited. The optimum extraction time was found to be 30 min and the detection limits were between 0.2 and 50 microg/l. Low concentrations of accompanying organic matter did not impair these limits. One of the main pharmaceutical contaminants found in ground and river water around Leipzig (Germany) was ibuprofen, with a concentration in the ng/l range. The enantioselective metabolism of ibuprofen was investigated.

At-line microextraction by packed sorbent-gas chromatography–mass spectrometry for the determination of UV filter and polycyclic musk compounds in water samples

An at-line analysis protocol is presented that allows the determination of four UV filters, two polycyclic musk compounds and caffeine in water at concentration level of ng L(-1). The fully automated method includes analytes enrichment by Microextraction by packed sorbent (MEPS) coupled directly to large volume injection-gas chromatography-mass spectrometry. Two common SPE phases, C8 and C18, were examined for their suitability to extract the target substances by MEPS. The analytes were extracted from small sample volumes of 800 microL with recoveries ranging from 46 to 114% for the C8-sorbent and 65-109% for the C18-sorbent. Limits of detection between 34 and 96 ng L(-1) enable the determination of the analytes at common environmental concentration levels. Both sorbents showed linear calibration curves for most of the analytes up to a concentration level of 20 ng mL(-1). Carryover was minimized by washing the sorbents 10 times with 100 microL methanol. After this thorough cleaning, the MEPS are re-used and up to 70 analyses can be performed with the same sorbent. The fully automated microextraction GC-MS protocol was evaluated for the influence of matrix substances typical for wastewater. Dilution of samples prior to MEPS is recommended when the polar caffeine is present at high concentration. Real water samples were analyzed by the MEPS-GC-MS method and compared to standard SPE.

Non-porous membrane-assisted liquid–liquid extraction of UV filter compounds from water samples

A method for the determination of nine UV filter compounds [benzophenone-3 (BP-3), isoamyl methoxycinnamate, 4-methylbenzylidene camphor, octocrylene (OC), butyl methoxydibenzoylmethane, ethylhexyl dimethyl p-aminobenzoate (OD-PABA), ethylhexyl methoxycinnamate (EHMC), ethylhexyl salicylate and homosalate] in water samples was developed and evaluated. The procedure includes non-porous membrane-assisted liquid-liquid extraction (MALLE) and LC-atmospheric pressure photoionization (APPI)-MS/MS. Membrane bags made of different polymeric materials were examined to enable a fast and simple extraction of the target analytes. Among the polymeric materials tested, low- and high-density polyethylene membranes proved to be well suited to adsorb the analytes from water samples. Finally, 2 cm length tailor-made membrane bags were prepared from low-density polyethylene in order to accommodate 100 microL of propanol. The fully optimised protocol provides recoveries from 76% to 101% and limits of detection (LOD) between 0.4 ng L(-1) (OD-PABA) and 16 ng L(-1) (EHMC). The interday repeatability of the whole protocol was below 18%. The effective separation of matrix molecules was proved by only marginal matrix influence during the APPI-MS analysis since no ion suppression effects were observed. During the extraction step, the influence of the matrix was only significant when non-treated wastewater was analysed. The analysis of lake water indicated the presence of seven UV filter compounds included in this study at concentrations between 40 ng L(-1) (BP-3) and 4381 ng L(-1) (OC). In non-treated wastewater several UV filters were also detected at concentration levels as high as 5322 ng L(-1) (OC).

Determination of organic priority pollutants and emerging compounds in wastewater and snow samples using multiresidue protocols on the basis of microextraction by packed sorbents coupled to large volume injection gas chromatography-mass spectrometry analysis.

This paper describes the development and validation of a new procedure for the simultaneous determination of 41 multi-class priority and emerging organic pollutants in water samples using microextraction by packed sorbent (MEPS) followed by large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS). Apart from method parameter optimization the influence of humic acids as matrix components on the extraction efficiency of MEPS procedure was also evaluated. The list of target compounds includes polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phthalate esters (PEs), nonylphenols (NPs), bisphenol A (BPA) and selected steroid hormones. The performance of the new at-line microextraction-LVI-GC-MS protocol was compared to standard solid-phase extraction (SPE) and LVI-GC-MS analysis. LODs for 100 mL samples (SPE) ranged from 0.2 to 736 ng L(-1) were obtained. LODs for 800 microL of sample (MEPS) were between 0.2 and 266 ng L(-1). In the case of MEPS methodology even a sample volume of only 800 microL allowed to detect the target compounds. These results demonstrate the high sensitivity of both procedures which permitted to obtain good recoveries (>75%) for all cases. The precision of the methods, calculated as relative standard deviation (RSD) was below 21% for all compounds and both methodologies. Finally, the developed methods were applied to the determination of target analytes in various samples, including snow and wastewater.

Development of a simultaneous pressurised-liquid extraction and clean-up procedure for the determination of UV filters in sediments

A useful tool for the determination of eight UV filters in sediments which combines extraction and clean-up in a single-step has been developed. To this end, the protocol incorporates silica gel and copper powder placed directly in the pressurised-liquid extraction (PLE) cell. After extract evaporation, salicylate- and benzophenone-type UV filters are derivatised with N,O-bis-trimethylsilyltrifluoroacetamide (BSTFA). Trimethylsilylation increases the sensitivity of these UV filters about 4-10-fold when they are finally analysed by gas chromatography-mass spectrometry (GC-MS). Derivatisation conditions (temperature, time and volume of BSTFA) and PLE parameters (temperature, time, number of cycles and solvent composition) were optimised using multivariate experimental designs. Under optimal conditions, the developed procedure provides an excellent linearity, detection limits (1-5 ng g(-1)) and recoveries above 73% for all the compounds. Compared to the few existing methods, this analytical approach affords optimal throughput and method automation. Finally, the proposed method was applied to the analysis of three sediment samples.

Metabolization of the Bacteriostatic Agent Triclosan in Edible Plants and its Consequences for Plant Uptake Assessment

Persistent environmental contaminants may enter agricultural fields via the application of sewage sludge, by irrigation with treated municipal wastewater or by manuring. It has been shown that such contaminants can be incorporated into crop plants. The metabolism of the bacteriostatic agents triclocarban, triclosan, and its transformation product methyl triclosan was investigated after their uptake into carrot cell cultures. A fast metabolization of triclosan was observed and eight so far unknown phase II metabolites, conjugates with saccharides, disaccharides, malonic acid, and sulfate, were identified by liquid chromatography-mass spectrometry. Triclocarban and methyl triclosan lack a phenolic group and remained unaltered in the cell cultures. Phase I metabolization was not observed for any of the compounds. All eight triclosan conjugates identified in the cell cultures were also detected in extracts of intact carrot plants cultivated on triclosan contaminated soils. Their total amount in the plants was assessed to exceed the amount of the triclosan itself by a factor of 5. This study shows that a disregard of conjugates in studies on plant uptake of environmental contaminants may severely underestimates the extent of uptake into plants and, eventually, the potential human exposure to contaminants via food of plant origin.

Fully automated determination of parabens, triclosan and methyl triclosan in wastewater by microextraction by packed sorbents and gas chromatography–mass spectrometry

A fully automated method for the determination of triclosan (TCS), its derivative methyl triclosan (MeTCS) and six parabens (esters of 4-hydroxybenzoic acid) including branched and linear isomers of propyl (i-PrP and n-PrP) and butyl paraben (i-BuP and n-BuP) in sewage water samples is presented. The procedure includes analytes enrichment by microextraction by packed sorbent (MEPS) coupled at-line to large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS). Under optimised conditions, compounds were extracted from 2 mL samples, adjusted at pH 3, using a C18 MEPS-sorbent. Adsorbed analytes were eluted directly into the Programmable Temperature Vaporizer (PTV) injector of the chromatograph with 2×25 μL of ethyl acetate. They were quantified using standard solutions in ultrapure water submitted to the same sample enrichment process as real sewage water samples. After signal normalisation using isotopic labelled species as internal surrogates, no differences were noticed among the extraction efficiency for sewage and ultrapure water; moreover, the proposed method reported lineal calibration curves from 0.1 to 10 ng mL(-1), relative standard deviations (%RSD) between 2 and 7.1% and limits of detection (LODs) varying from 0.001 to 0.015 ng mL(-1) in ultrapure water and from 0.02 to 0.59 ng mL(-1) in the most complex sample (raw wastewater).

Uptake of Galaxolide, Tonalide, and Triclosan by Carrot, Barley, and Meadow Fescue Plants

Many xenobiotics entering wastewater treatment plants are known to be persistent during wastewater treatment and tend to adsorb to sewage sludge. The application of sewage sludge as fertilizer in agriculture may pose the risk of an incorporation of xenobiotics in the cultivated plants and, finally, an inclusion into the food chain. This study was performed to investigate the uptake of common sewage sludge contaminants, galaxolide, tonalide, and triclosan, by plants used for human consumption and livestock feeding. Barley, meadow fescue, and four carrot cultivars were sown and grown in spiked soils under greenhouse conditions. After harvesting the plants, roots and leaves were analyzed separately, and the respective bioconcentration factors were calculated. In carrots, a concentration gradient of the xenobiotics became evident that decreased from the root peel via root core to the leaves. A significant influence of the differing root lipid contents on the uptake rates cannot be supported by our data, but the crucial influence of soil organic carbon content was confirmed. Barley and meadow fescue roots incorporated higher amounts of the target substances than carrots, but translocation into the leaves was negligible. The results indicated that an introduction of persistent semi- and nonpolar xenobiotics into the food chain via edible plants like carrots could be of certain relevance when sludge is applied as fertilizer. Due to low rates found for the translocation of the xenobiotics into the aerial plant parts, the entrance pathway into food products via feeding livestock is less probable.

Pressurised membrane-assisted liquid extraction of UV filters from sludge.

A method for the determination of 11 UV-filter compounds in sludge has been developed and evaluated. The procedure includes the use of non-porous polymeric membranes in combination with pressurised liquid extraction (PLE). Firstly, the solid sample, wetted with the extraction solvent, was enclosed into tailor-made bags prepared with low density polyethylene. Secondly, these packages were submitted to a conventional PLE (70 degrees C, 4 cycles of 5 min static time). Finally, the analytes were determined by liquid chromatography-atmospheric pressure photoionisation-tandem mass spectrometry. The main advantage of this procedure is the reduction of time, solvent and labour effort ought to the combination of extraction and clean-up in a single step. Although the extraction is not quantitative (thus, standard addition is recommended for quantification) selectivity is clearly gained using the membrane as a consequence of the differences of permeation and transport through the membrane between the analytes and other sample matrix components. The optimised protocol provides limits of detection ranging from 0.3 ng g(-1) (ethylhexyl dimethyl p-aminobenzoate (OD-PABA)) to 25 ng g(-1) (ethylhexyl triazone (EHT)) with only 0.5 g of sludge sample. All the studied UV filters were found in the samples at concentration levels between 1.4 and 2479 ng g(-1), emphasising the high adsorption potential of this kind of environmental pollutants onto solid samples such as sludge. Also, this method has permitted the determination of seven of the studied UV filters in sludge samples for the first time.