Lennart Mårtensson

Occurrence and removal of pharmaceuticals in a municipal sewage treatment system in the south of Sweden

The occurrence and removal rate of seven pharmaceuticals (ibuprofen, naproxen, diclofenac, fluoxetine, ofloxacin, norfloxacin, ciprofloxacin), two metabolites (norfluoxetine, clofibric acid), one degradation product (4-isobutylacetophenone) and 3 estrogens (17alpha-ethinylestradiol, 17beta-estradiol, estrone) were studied in the inlet and outlet of a tertiary sewage treatment plant (STP) in Sweden as well as between different treatment steps in the STP which includes a conventional activated sludge step. Pharmaceuticals in raw household and raw hospital sewage streams leading to the STP were as well investigated. Hydraulic retention times (HRT) of each treatment step was considered for sampling and for the calculation of the removal rates. These rates were above 90%, except for diclofenac, clofibric acid, estrone and ofloxacin. However, only diclofenac and naproxen showed significant effluent loads (>145 mg/d/1000 inh). Diclofenac was not eliminated during the treatment and in fact even higher concentrations were found at the effluent than in the inlet of the STP. 17alpha-Ethinylestradiol was not detected in any of the samples. Results indicate that a STP such as the one in Kristianstad, Sweden, with a tertiary treatment is sufficient to remove significantly most of the investigated pharmaceuticals. The chemical treatment improved the removal of several pharmaceuticals especially the antibiotics, which showed step removal rates between 55 and 70%. The expected concentration levels of the pharmaceuticals in the surface water (dilution 1 to 10) close to the outlet of the STP are below the no-observed effect-concentration (NOEC). However, despite that this would imply no important effects in the aquatic environment one cannot rule out negative consequences nearby the STP because most of the NOEC values are derived from acute toxicity data. This may underestimate the real impact of pharmaceuticals in the aquatic ecosystem.

The performance of a natural treatment system for landfill leachate with special emphasis on the fate of organic pollutants

A natural treatment system for the treatment of leachate was studied at Moskogen landfill in southern Sweden. This facility consists of three consecutive ponds and a soil-plant (SP)-system. A test area, receiving water from the third pond with the same hydraulic load as the SP-system, was used for estimation of the latter system. Quality parameters including biochemical oxygen demand, total organic carbon, ammonium, nitrate, orthophosphate, and total suspended solids along the treatment line were determined as well as soluble metals (Cu, Cd, Zn, Cr, Ni, and Pb). In addition a thorough investigation along the treatment line has also been performed concerning volatile organic compounds and semi-volatile organic compounds. Non-polar organic compounds were investigated using gas chromatography-mass spectrometry. Quantification was based on the assumption of equal response for the compounds found in comparison with the chosen marker substances. For polar, water-soluble compounds the measurements were restricted to phenolic compounds using high-performance liquid chromatography. Several different types of organic compounds were found in the raw leachate including aromatics, benzene-sulfonamides, biphenyls, naphthalene, organic phosphates, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, phenols and phthalates. The treatment system efficiently reduced organic pollutants, heavy metals, and nitrogen/phosphorous compounds. Most metals and organic compounds in the leachate were already significantly reduced to a low level in the treatment ponds and ammonium-N was efficiently transformed to nitrate-N in the SP-system.

Improved spectrophotometric vitellogenin determination via alkali-labile phosphate in fish plasma–a cost effective approach for assessment of endocrine disruption

Vitellogenin (VTG) is a well known protein biomarker for exposure to environmental estrogens and possible endocrine disruption in fish. VTG is very dominant in plasma after the onset of vitellogenesis and the protein is heavily phosphorylated. This enables indirect quantification through measurement of alkali-labile protein bound phosphate (ALP) as an alternative to the more expensive enzyme linked immunosorbent assay. Good correlation has previously been shown between ALP and actual VTG levels but little effort has been made to investigate the method in an analytical way e.g., to assure the origin of the measured phosphate. During this method development care has been taken to rule out non-VTG sources of phosphate such as phospholipids and free phosphate in the blood plasma. Sample preparation has been simplified and unnecessary steps have been omitted. The common spectrophotometric measurement for ALP involves measurement at two wavelengths and calculation of corrected absorbance values. With a quick phase separation step the spectrophotometric phosphate determination using molybdic acid and ascorbic acid has been improved and all matrix interference has been eliminated. The final ALP method presented here has a detection limit of 3.2 µg PO4 3−/ml plasma which is six times lower than similar methods and it also has less variability. A high sample throughput in comparison to previous ALP methods is possible after scaling down sample and reagent volumes to fit in a 96 well microtiter plate. The cost for buying all chemicals and plastic consumer goods for setting up the indirect protocol for the analysis of 1000 samples is only circa 350 euro. This is only 1% of the material cost for buying commercially available test kit for direct quantification of VTG in the same number of samples. The ALP method should thus be of interest also for applied scientists outside advanced research laboratories.

Leachability testing of metallic wastes.

The performance of two tests, a batch test and a percolation test for the characterization of waste as suggested in the EU council decision 2003/33/EC was investigated. The tests were carried out on two solid waste streams from a metal recycling industry. The concentrations of heavy metals such as Cu, Znand Pb were more than one order of magnitude lower than the proposed limit values. Generally, batch test values were equal or higher than percolation test values. With the proposed test procedures both materials could be considered as non-dangerous wastes. The test performance was also investigated using a leachant with higher ionic strength instead of demineralized water as prescribed. The results clearly show a significant increase in the concentration of some heavy metals. Total concentrations of phenolic compounds and polychlorinated biphenyls were less than 1 p.p.m. and 2 p.p.b., respectively. The precision of the batch and the percolation tests were on average 48 and 35%, respectively.

Development and application of an analytical protocol for evaluation of treatment processes for landfill leachates. II. Evaluation of leachate treatment efficiency of different steps in a constructed pilot plant

Different methods for treatment of leachate from a municipal solid waste (MSW) landfill were tested in a pilot plant. Raw leachate was pre-treated with aeration and sedimentation, followed by several parallel individual steps such as bioremediation, chemical oxidation, ozonation, and geo-bed filters. The efficiency of different treatment steps was evaluated according to one previously developed protocol, which includes measurements of several parameters such as conductivity, pH, nutrients, chloride, metals, organic compounds, and acute toxicity before and after a treatment step. The treatment steps which showed the highest efficiency towards organic pollutants in leachate were ozone treatment and chemical oxidation. The use of an adsorption filter, a geo-bed with a mixture of peat and bottom ash with ca 10% remaining carbon, also had good effects. A combination of pre-treatment and a geo-bed filter with peat and carbon ash gave the best overall treatment results when water-quality parameters such as total organic carbon and ammonia-nitrogen were also considered.

Emissions from baled municipal solid waste: II. Effects of different treatments and baling techniques on the emission of volatile organic compounds

This paper focuses on the volatile organic compound emissions from baled municipal solid waste (MSW). The analytical methodology was based on sampling with adsorbent tubes once a month during seven occasions within a time period of 1 year. Automated analyses were carried out on-line work-up with thermal desorption directly connected to a gas chromatograph-mass spectrometer. The effect of different baling techniques, cylindrical and rectangular baling was compared. It was found that cylindrically baled MSW emitted larger concentration of esters than their rectangular counter parts. Conversely, aromatic compounds emissions dominated in rectangularly baled MSW. This indicates that different degradation mechanisms operate in the waste bales. Cylindrical and rectangular bales are generally wrapped with six layers of 250 μm thick low density polyethylene (LDPE). It was observed that by wrapping an extra six layers of LDPE film onto the bales, the emissions from cylindrical bales increased while emissions from the rectangular counterpart decreased. Over time, the volatile organic compound emissions from cylindrical bales decreased two orders of magnitudes from 96.2 ± 20.8 μgm-3 in September 2003 to 0.80 ± 0.07 μgm-3 in July 2004. The rectangular bales exhibited an almost identical relative emission reduction from 54.4 ± 4.3 μgm-3 in September 2003 to 0.46 ± 0.02 μgm-3 in July 2004. Future work will concentrate on full-scale storages, taking into account waste type, storage size, temperature development and the different baling techniques among other variables.

Development and application of an analytical protocol for evaluation of treatment processes for landfill leachates : I. Development of an analytical protocol for handling organic compounds in complex leachate samples

A strategy is presented for evaluation of treatment procedures for landfill leachate with emphasis on organic pollutants. An analytical scheme, the LAQUA protocol, was developed as a guide for the analytical work. The protocol includes organic as well as metals, inorganic ions, water-quality parameters, and toxicity. The proposed strategy considers the behaviour of both polar and non-polar organic substances at trace levels. For polar substances, phenols were chosen as markers and determined with an automated supported liquid membrane extraction device, coupled on-line to HPLC with a diode-array detector. For non-polar substances, PCBs and 10 unidentified compounds were chosen as markers and analysed by solid-phase extraction combined with supercritical fluid extraction with GC analysis. The chosen measurement strategy, based on the use of marker substances, difference measurements, and versatile data-handling procedures, provided essential information about complex systems at relatively low cost.

Column studies aiming at identification of suitable filter materials for pollutant removal from landfill leachate

Landfill leachate contains a complex mixture of inorganic and organic pollutants, which need to be removed before they pollute the environment. Different filter media (peat mixed with either carbon-containing ash, polyurethane waste, or wood pellets) were investigated with respect to their possibility to simultaneously and at low initial concentrations remove metals, polar and non-polar organic compounds. The mixture of peat and carbon-containing ash was found to be the best medium. Reduction in leachate of phenolic substances was 96%, of PBDEs was over 98%, of DOC 40% and of important metals as Cu, Pb and Sn 60%, 90% and 93%, respectively.

Emissions from baled municipal solid waste: I. Methodological approach for investigation of gaseous emissions

This paper presents a methodological approach for the study of volatile organic compounds (VOCs) in air, emitted during storage of municipal solid waste in bales. Determination of VOCs was based on sampling with adsorbent tubes followed by automated analysis using on-line work-up with a thermal desorption unit directly connected to a gas chromatograph–mass spectrometer. Using calculation algorithms and multidimensional statistical analysis of large amounts of data collected, the information was compressed and visualized. The approach was applied to initial measurements of emissions of VOCs from 24 bales composed of municipal solid waste, each bale stored in a wooden box. These bales were produced using the two types of baling equipment available, resulting in cylindrical or rectangular bales, with different densities. Hundreds of different VOCs emitted from these bales sorted out into groups with different chemical structure. Differences in VOC concentrations in air were found between wastes stored in cylindrical or rectangular bales. For instance, it was found that the concentration of VOCs (relative to the concentration of toluene), in the first experiment after storing, for cylindrical bales with six layers of LDPE was 115 ± 10 μg m-3, while for rectangular bales it was only 64 ± 8 μg m-3. The procedure used for data interpretation suggested different degradation mechanisms in different types of bales. The use of multiple data interfaces, multidimensional statistics and automated chemical analysis methods are likely to be more and more common for waste companies and waste research in the near future. This is due to the interdisciplinary nature of the subject that relies heavily on various areas of science and information technology.

Filter-based treatment of leachate from an industrial landfill containing shredder residues of end-of-life vehicles and white goods.

A pilot plant was set up to treat leachate from an industrial landfill containing shredder residues of end-of-life vehicles and white goods. The treatment plant consisted of aeration and sedimentation steps for pre-treatment, and a filter. The plant was designed to simultaneously remove various types of pollutants. The efficiencies of pre-treatment and of the main treatment step were investigated over a period of 3 years at the landfill site. By continuous aeration of the leachate the concentrations of Fe and Mn were reduced by 55% and 49%, respectively. By prolonged sedimentation suspended solid content was noticeably reduced (72%). In the filter, consisting of a mixture of peat and carbon-containing ash as a treatment medium, very high reduction of polar organic compounds, e.g. phenol (74%), o-and p-cresol (91%), and 2,4-dimethylphenol (73%), high average reduction of metals, e.g. Pb (78%), Fe (74%), Cu (73%), Mn (56%), Sn (55%), and Zn (47%), and good average reduction of DOC (26%), Tot-N (23%) and NH4-N (46%) were achieved. Sixty non-polar compounds in the leachate, identified by GC-MS screening, occurred at trace level. Most of them were considerably reduced in the filter.