Susanne Jonsson

Transport and release of chemicals from plastics to the environment and to wildlife.

Plastics debris in the marine environment, including resin pellets, fragments and microscopic plastic fragments, contain organic contaminants, including polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons, petroleum hydrocarbons, organochlorine pesticides (2,2′-bis(p-chlorophenyl)-1,1,1-trichloroethane, hexachlorinated hexanes), polybrominated diphenylethers, alkylphenols and bisphenol A, at concentrations from sub ng g–1 to µg g–1. Some of these compounds are added during plastics manufacture, while others adsorb from the surrounding seawater. Concentrations of hydrophobic contaminants adsorbed on plastics showed distinct spatial variations reflecting global pollution patterns. Model calculations and experimental observations consistently show that polyethylene accumulates more organic contaminants than other plastics such as polypropylene and polyvinyl chloride. Both a mathematical model using equilibrium partitioning and experimental data have demonstrated the transfer of contaminants from plastic to organisms. A feeding experiment indicated that PCBs could transfer from contaminated plastics to streaked shearwater chicks. Plasticizers, other plastics additives and constitutional monomers also present potential threats in terrestrial environments because they can leach from waste disposal sites into groundwater and/or surface waters. Leaching and degradation of plasticizers and polymers are complex phenomena dependent on environmental conditions in the landfill and the chemical properties of each additive. Bisphenol A concentrations in leachates from municipal waste disposal sites in tropical Asia ranged from sub µg l–1 to mg l–1 and were correlated with the level of economic development.

Analysis of mono- and diesters of o-phthalic acid by solid-phase extractions with polystyrene–divinylbenzene-based polymers

Retention mechanisms of an unmodified and a hydroxylated polystyrene-divinylbenzene polymer were studied by solid-phase extraction of o-phthalic acid and some of its mono- and diesters from purified water and then analysing by GC-MS. The monoesters and phthalic acid were retained only when protonated (i.e. acidified with HCI to pH 0.9). Of all elution solvents tested, ethyl acetate gave the best overall recoveries (61-89%) with both polymers. Applicability to complex matrixes (e.g. acidogenic landfill leachates) was examined by introducing a washing step with acetone in acidified water (pH 0.9) to eliminate volatile fatty acids (C2-C6) from the cartridge. Finally, the method was tested on real samples.

Mono- and diesters from o-phthalic acid in leachates from different European landfills

Leachates from 17 different landfills in Europe were analysed with respect to phthalates, i.e. phthalic acid diesters (PAEs) and their degradation products phthalic acid monoesters (PMEs) and ortho-phthalic acid (PA). Diesters are ubiquitous and the human possible exposure and potential to human health and environment has put them in focus. The aim of this study was to elucidate whether monoesters and phthalic acid could be traced in landfill leachates and in what concentrations they may be found. The results showed that phthalates were present in the majority of the leachates investigated. The monoesters appeared from 1 to 20 microg/L and phthalic acid 2-880 microg/L (one divergent value of 19 mg phthalic acid/L). Their parental diesters were observed from 1 to 460 microg/L. These observed occurrences of degradation products, of all diesters studied, support that they are degraded under the landfill conditions covered by this study. Thus, we have presented strong evidences to conclude that microorganisms in landfills degrade diesters released from formulations in a variety of products, including polyvinyl chloride (PVC) species.

Quantification of volatile sulfur compounds in complex gaseous matrices by solid-phase microextraction

Procedures were assessed for quantifying nine volatile sulfur compounds found in complex gaseous samples collected at a biogas-production plant and a sewage treatment plant. The target compounds were extracted by solid-phase microextraction (using the 75-microm Carboxen-polydimethylsiloxane fiber coating) at 22 degrees C for 20 min, and analyzed by GC-MS. Detection limits ranged between 1 pptv (v/v) for carbon disulfide and 470 pptv (v/v) for hydrogen sulfide. High amounts of organic compounds were found during full-scan analysis of the samples and standard additions to individual sub-samples revealed that the analysis was subject to matrix effects. However, the functions obtained by standard additions were still linear and quantification was possible for all the compounds tested except hydrogen sulfide. No detectable losses were observed during storage in the sampling containers, made of Tedlar film, over a storage period of 20 h. However, water permeated through the walls and the relative humidity in the bag increased during storage until it reached the ambient level. Finally, it was shown that the drying agent, CaCl2, caused no detectable losses of any of the compounds.

Toxicity of mono- and diesters of o-phthalic esters to a crustacean, a green alga, and a bacterium

The degradation of phthalic acid diesters may lead to formation of o-phthalic acid and phthalic acid monoesters. The ecotoxic properties of the monoesters have never been systematically investigated, and concern has been raised that these degradation products may be more toxic than the diesters. Therefore, the aquatic toxicity of phthalic acid, six monoesters, and five diesters of o-phthalic acid was tested in three standardized toxicity tests using the bacteria Vibrio fischeri, the green algae Pseudokirchneriella subcapitata, and the crustacean Daphnia magna. The monoesters tested were monomethyl, monoethyl, monobutyl, monobenzyl, mono(2-ethylhexyl), and monodecyl phthalate, while the diesters tested were dimethyl, diethyl, dibutyl, butylbentyl, and di(2-ethylhexyl)phthalate, which were assumed to be below their water solubility. The median effective concentration (EC50) values for the three organisms ranged from 103 mg/L to >4.710 mg/L for phthalic acid, and corresponding values for the monoesters ranged from 2.3 mg/L (monodecyl phthalate in bacteria test) to 4,130 mg/L (monomethyl phthalate in bacteria test). Dimethyl and diethyl phthalate were found to be the least toxic of the diesters (EC50 26.2-377 mg/L), and the toxicity of the other diesters (butylbenzyl and dibutyl phthalate) ranged from 0.96 to 7.74 mg/L. In general, the phthalate monoesters (degradation products) were less toxic than the corresponding diesters (mother compounds).

Behaviour of mono- and diesters of o-phthalic acid in leachates released during digestion of municipal solid waste under landfill conditions

In order to investigate phthalates in landfill leachates, four landfill simulation reactors, filled with municipal solid waste from a housing area, were studied. Plasticised polyvinyl chloride (PVC) was added to two of the reactors. Two reactors, one with and one without the additional PVC, were aerated for 3 months to achieve methanogenic conditions. The other two became acidogenic a few days after filling and closing. After approximately 3 years, the acidogenic waste became methanogenic. The leachates were analysed for phthalic acid diesters and their degradation products, phthalic acid monoesters and o-phthalic acid. The occurrence of monobenzyl phthalate (MbenzP) and mono(2-ethylhexyl) phthalate (MEHP) showed that the diesters, butylbenzyl phthalate (BBP) and di(2-ethylhexyl) phthalate (DEHP), released from the PVC products had been transformed, and that they were not completely sorbed to particles or to the waste material. Monoesters were observed once methanogenic conditions were established. The monoesters and phthalic acid were present in concentrations several orders of magnitude higher than the diesters themselves. Our results show that it is important to include monoesters in studies of the fate of diesters. To date, monoesters have been neglected in investigations of organic pollutants in landfill leachates.

Modelling MSW decomposition under landfill conditions considering hydrolytic and methanogenic inhibition

A landfill typically progresses through a series of microbial degradation phases, in which hydrolysis, production and consumption of fermentation products, such as fatty acids, and methane formation play important roles. For ultimate degradation of the waste, stable methanogenic conditions have to be attained, and maintained for sufficient time. Using experimental data from 100-L landfill simulation reactors containing municipal solid waste from a residential area, a distributed model, which accounts for vertical water flow, was developed. As a first step, the waste was divided into two fractions: readily degradable and recalcitrant waste. Secondly, the general hydrolysis of the recalcitrant waste was accounted for by including a specific, well-defined chemical substance in the model that generally occurs in Municipal Solid Waste (MSW) and is hydrolysed before its further degradation to methane. For this purpose we chose diethyl phthalate and its hydrolysis product monoethyl phthalate, for which leachate data are available from the reactors. The model indicated that inhibition of the hydrolytic and methanogenic processes occurred during␣the acidogenic phase and that it could be overcome either by improving the chemical environment or by the complete oxidation of the inhibiting, i.e. the easily degraded, fraction of the waste. The generality of the model was confirmed by the patterns of the phthalate di- and monoester transformations obtained. The validity of the model was further confirmed using experimental data from parallel reactors, which were subjected to either leachate exchange with an already methanogenic reactor or to initial aeration to force the reactor into stable methanogenic conditions.

Transformation of phthalates in young landfill cells

Phthalic acid diesters are additives in a variety of materials that can end up in landfills. Leachates from a series of full-scale young landfill cells were analysed over time for dimethyl, diethyl, dibutyl, butylbenzyl, and di(2-ethylhexyl) phthalate (respectively designated DMP, DEP, DBP, BBP, and DEHP), and their corresponding monoesters monomethyl, monoethyl, monobutyl, monobenzyl, and mono(2-ethylhexyl) phthalate (MMP, MEP, MbutP, MbenzP, and MEHP, respectively), as well as o-phthalic acid (PA). One landfill cell was created in each of three consecutive years by deposition of the same type of waste in July and August. The pH, volatile fatty acids (VFAs), and total organic carbon (TOC) were measured to characterise development of the degradation phases in three landfill cells, which revealed early acidogenic to initial methanogenic stages. Analysis of the phthalate compounds showed that observed concentrations of the degradation products were below the detection limit in the acidogenic leachates but exceeded concentrations of their corresponding diesters in leachates from cells in the initial methanogenic phase. Maximum and average concentrations of phthalic acid were 50 and 23 mg/l, respectively, and the corresponding values for the other phthalates were 430 and 27 microg/l. The concentrations of all phthalates decreased during the establishment of stable methanogenic conditions.

Chemical characterisation of adsorbable organic halogens (AOX) in precipitation

The average concentration of AOX (adsorbable organic halogens) in precipitation was found to vary from 2 – 3 µg Cl/L at remote sites in northern Sweden and Finland to approximately 10 µg Cl/L further to the south in the Baltic Sea region. By using different methods to concentrate and fractionate dissolved organic substances, this group of substances was characterised with respect to volatility, polarity and occurrence of specific organochlorine and organobromine compounds. Aqueous phases were analysed for the group parameters AOX and TOC (total organic carbon). Organic phases were analysed for the total amount of organohalogens and by gas Chromatographic procedures employing different detectors, mainly the element-specific atomic emission detector (AED) and mass spectrometry (MS). The results obtained showed that AOX in precipitation are mainly non-volatile. Furthermore, neutral compounds were found to dominate, and precipitation AOX thereby differ from surface water AOX. A substantial part of the AOX in precipitation were efficiently adsorbed to the non-ionic adsorbent XAD-8 and almost quantitatively desorbed by organic solvents. However, the gas Chromatographic analyses of different extracts of organic substances showed that chloroacetic acids were the only specific compounds that contributed significantly to AOX in precipitation. A few other organochlorine compounds, probably released from local sources, were present in ppt concentrations.

Organohalogens of natural or unknown origin in surface water and precipitation

Abstract Information about the occurrence and chemical character of adsorbable organic halogens (AOX) in surface water and precipitation is reviewed and updated with results from on‐going studies. There is now very strong evidence that the widespread occurrence of AOX in unpolluted aquatic environments is primarily caused by naturally halogenated humic substances; and, recently, the first chlorinated structural elements in aquatic fulvic acids were identified. Despite the considerable amounts of high‐molecular‐weight organohalogens in humus‐rich surface waters, the concentrations of specific low‐molecular‐weight organohalogens are generally low. This is illustrated by chromatograms obtained by combining different enrichment procedures for trace organics in water with GC‐AED analysis (gas chromatography with atomic emission detection) of chlorinated and brominated compounds. On‐going studies of the chemical character of AOX in precipitation have shown that the compounds responsible for the major fraction o...