Pia Lassen

Characterisation of humic materials of different origin: A multivariate approach for quantifying the latent properties of dissolved organic matter

The inherent chemical properties of eight different dissolved organic matters (DOMs) originating from soil, surface and groundwater have been analysed. The samples consist of isolated fulvic acids (FA), humic acids (HA), and humic substances (HS), i.e. natural mixtures containing a humic and a fulvic fraction. The humic substances have been characterised by elemental analysis, size exclusion chromatography, E2/E3 and E4/E6 UV absorption ratios, and liquid-state 13C-NMR spectroscopy. The information contents of the different analytical methods have been investigated by pattern recognition, i.e. cluster analysis and principal component analysis (PCA). A comparative study of the information contents of DOM descriptors derived from different analytical methods is presented. Through extraction of information content of the individual analytical methods the inherent properties of DOM are quantified. Pattern recognition revealed significant quantitative differences in the inherent properties of DOM of different origin and type. PCA based on the NMR descriptors showed highest explained variance. However, all models showed low robustness due to the limited number of samples. The supervised pattern recognition, i.e. PCA, indicates a classification of DOMs into groups of similar properties by an increase in the number of samples. Furthermore that the number of groups may be higher and more continuously distributed than the conventional classification into fulvic acids, humic acids or humic substances.

Concentrations of anticoagulant rodenticides in stoats Mustela erminea and weasels Mustela nivalis from Denmark.

Anticoagulant rodenticides are widely used to control rodent populations but they also pose a risk of secondary poisoning in non-target predators. Studies on anticoagulant rodenticide exposure of non-target species have mainly reported on frequency of occurrence. They have rarely analyzed variations in residue concentrations. We examine the occurrence and concentrations of five anticoagulant rodenticides in liver tissue from 61 stoats (Mustela erminea) and 69 weasels (Mustela nivalis) from Denmark. Anticoagulant rodenticides were detected in 97% of stoats and 95% of weasels. 79% of the animals had detectable levels of more than one substance. Difenacoum had the highest prevalence (82% in stoats and 88% in weasels) but bromadiolone was detected in the highest concentrations in both stoat (1.290 μg/g ww) and weasel (1.610 μg/g ww). Anticoagulant rodenticide concentrations were highest during autumn and winter and varied with sampling method. Anticoagulant rodenticide concentrations were higher in stoats and weasels with unknown cause of death than in specimens killed by physical trauma. There was a negative correlation between anticoagulant rodenticide concentrations and body condition. Our results suggest that chemical rodent control in Denmark results in an extensive exposure of non-target species and may adversely affect the fitness of some stoats and weasels.

Solubilization of phenanthrene by humic acids

Abstract Humic acids has a distinct solubilizing effect on phenanthrene. The rate constant for the dissolution of solid phenanthrene in synthetic groundwater is increased by ca. 50% in the presence of 50 mg/L humic acids. The phenanthrene - humic acid interactions was found to depend significantly on the actual humic acid concentration since a pronounced decrease in the interaction constant, as well as in the water - organic matter partitioning coefficient was observed with increasing humic acid concentration. The effects are discussed in terms of concentration dependent macromolecular structural changes in the humic acids, as are effects of varying pH and ionic strength conditions of the aqueous phase.

Formation of organic chlorine compounds of low molecular weight in the chloroperoxidase-mediated reaction between chloride and humic material

This paper describes the formation of organic chlorine compounds like chloroform, and chlorinated acetic acids, acetones, pyruvic acids, maleic and fumaric acids, acetonitriles and acetamides in the chloroperoxidase-mediated reaction between chloride and humic material Chemical chlorination may also occur to a small extent, because hydrogen peroxide may give rise to active chlorine. Since soil contains all the necessary precursors, enzymatic chlorination is a plausible mechanism for the formation of organic chlorine compounds in the terrestrial environment.

Reverse quantitative structure-activity relationship for modelling the sorption of esfenvalerate to dissolved organic matter: A multivariate approach

The sorption of the pyrethroid, esfenvalerate, to the dissolved and/or dispersed fraction of eight different natural humic compounds has been investigated. The dissolved organic matters (DOMs) included in this study originate from ground water, soil pore water, and surface waters. Sorption was modelled at DOM concentration levels where equilibrium partitioning of esfenvalerate between DOM and the aqueous bulk phase prevails. The inherent characteristics of the eight different humic materials, quantified in the preceding paper by Thomsen et al. (2002, this issue (PII: S0045-6535(02)00335-1)), have been used as explanatory variables for modelling this equilibrium partitioning. Using a reverse QSAR approach based on by projection-into-latent-structure regression (PLS-R) inherent sorbent properties determining for the sorption affinity of esfenvalerate to DOM were analysed. For all humic substances a decrease in the DOM-normalised equilibrium-partitioning coefficient, K(DOM), with increasing concentration of DOM was observed. Significant variations in K(DOM) values, as function of the inherent characteristics of the individual humic substances, were found at DOM concentrations of 75 and 100 ppm, respectively. The latter is a strong indication of variations in sorption mechanisms of esfenvalerate to DOM of varying inherent properties. Groupings in the principal property space quantifying DOMs may indicate that separate models are needed for quantifying the equilibrium partitioning to different classes of DOM.

14C and 125I Labelling of Humic Material for Use in Environmental Studies

Abstract Humic and fulvic acids are present in nearly all natural waters. These acids are known to affect the transport of environmental contaminants such as metals and hydrophobic organics through the terrestrial environment. an understanding of their role in the transport of contaminants is therefore essential and is facilitated if the acid is labelled with a suitable radioactive label. This paper reports the use of 14C-methylamine and 125I to label humic acid with either 14C or 125I and investigates factors which affect the yield of these reactions. the stability and mobility of the labelled humic material through sand is also reported.

Enzymatically mediated incorporation of 2-chlorophenol and 4-chlorophenol into humic acids

Abstract A possible route to chlorinated humic substances in the environment, is an indirect chlorination of humic material by enzymatically mediated incorporation of low molecular weight organo-chlorine compounds into the humic skeleton. The enzymatically mediated incorporation of 2-chlorophenol and 4-chlorophenol into humic acids by Horseradish Peroxidase is reported. The incorporation is accompanied by a significant polymerization of the chlorophenols. The stability of the chlorinated humic acids as well as the environmental implication are discussed.

Enzymatically mediated formation of chlorinated humic acids

Abstract A commercially available humic acid (HA) was chlorinated by chloride ions in the presence of the enzyme chloroperoxidase and hydrogen peroxide. The resulting chlorinated HA showed a uniform distribution of chlorine independent of the single molecular weight fractions. The chlorination of HA has been studied as a function of enzyme-, hydrogen peroxide-, and chloride concentrations. The elimination of free chloride/low molecular weight chloroorganics upon dissolution of isolated chlorinated HA is discussed.

Endocrine-Disrupting Effects of Compounds in Danish Streams

Effluents from municipal wastewater-treatment plants and scattered dwellings, as well as runoff from agricultural fields, are sources of endocrine-disrupting compounds (EDCs) in the aquatic environment. The present study investigated the correlation between the occurrence of EDCs in nine Danish streams using passive samplers (polar organic integrative samplers and silicone membranes) and determined their possible biological effects as assessed by mammal cell cultures and the mussel (Unio tumidus). The passive samplers and mussels were exposed simultaneously at the study sites. The extracts from the passive samplers were used to measure the concentrations of EDCs and the biological effects on the estrogen (ER), androgen (AR), and aryl hydrocarbon (AhR)-receptor transactivation. Male mussels were investigated for biomarkers of endocrine effects, such as the levels of vitellogenin-like proteins measured as alkali-labile phosphate (ALP). EDC concentrations, hormone-receptor transactivation (ER, AR, AhR), and level of ALP were greater downstream of wastewater-treatment plants compared with upstream sites and sites supposed to be relatively nonimpacted by wastewater. Furthermore, there was a significant positive correlation between in vitro AhR transactivation and frequency of ALP of male mussels. We conclude that wastewater effluent is an important source of endocrine-disrupting effects in the aquatic environment and that the combination of biological effect measurements and chemical analyses based on passive sampling is useful in the assessment of the ecological state of the aquatic environment.

Polychlorinated biphenyls, organochlorine pesticides and polycyclic aromatic hydrocarbons in a one-off global survey of bivalves.

During the Danish Galathea 3 expedition, bivalve samples were collected at the Faroe Islands, Greenland, Ghana, South Africa, Australia, Solomon Islands, New Zealand, Chile, US Virgin Islands, Boston, Newfoundland and Shetland Islands and analysed for organochlorines and PAHs. Concentration differences of up to three orders of magnitude were observed, with the highest concentrations at Boston harbour (SPCB 338 ng g(-1) dw, ΣSPAH 5966 ng g(-1) dw) and the Sydney estuary (ΣSPCB 282 ng g(-1) dw, SPAH 1453 ng g(-1) dw). Local impacts were also found for the Greenland capital Nuuk in terms of PCB and PAH levels, while other Greenland samples came closest to representing PAH background levels. Several locations had undetectable organochlorine levels, including Hobart and Chile, which had the lowest SPAH concentrations (<200 ng g(-1) dw). It was possible to group the stations according to their pyrogenic/petrogenic influence using Principal Component Analyses, and indications of petroleum sources were found at Nuuk.