Mathias Ricking

A guidance for the assessment and evaluation of sediment quality a German Approach based on ecotoxicological and chemical measurements

The recommendations presented in this paper use an integrated hierarchical approach combining toxicological, chemical and ecological information to assess and evaluate the quality of sediments. For this reason, biological methods, in combination with the tools of chemical analysis, are given priority when examining the quality of the sediment to establish adverse effects. The trigger is the biotest, instead of chemical methods commonly used. The individual methods are presented for a German approach and can be adopted to other countries by applying ISO, OECD methods. Support is provided on how to best integrate data generated using different assessment tools. Keywords: Bioassays; biological and chemical analysis; ecotoxicology; integrated assessment; sediment assessment; sediment quality; stepwise strategy

Molecular markers of anthropogenic activity in sediments of the Havel and Spree Rivers (Germany)

Detailed gas chromatographic/mass spectrometric analyses have been applied to sediment samples of the Havel and Spree River, tributaries to the Elbe River, in order to identify specific molecular markers of anthropogenic activities. Despite a wide variety of lipophilic organic compounds from diffuse anthropogenic contamination, a local emission of an industrial point source was reflected by specific markers including halogenated compounds and nitrogen containing substances (4-ethylnitrobenzene, formyl piperidine, acetyl piperidine). In addition to well-known anthropogenic markers various new molecular tracers were detected and are discussed, namely plasticizers (alkylsulfonic acid aryl esters, tributyl and tricresyl phosphates), synthetic fragrances (galaxolide, tonalide, 4-oxoisophorone), additives of personal care products (4-methoxycinnamic acid 2-ethylhexyl ester, benzyl benzoate, dibenzyl ether, benzophenone), occurring due to sewage treatment plant input.

Polycyclic aromatic musk compounds in sewage treatment plant effluents of Canada and Sweden--first results.

Polycyclic musk fragrances (PMF) are widely used fragrances for cosmetics and other personal and household care products. Quantitative data on PMF (HHCB-Galaxolide, AHTN-Tonalide, ATTI-Traseolide, AHMI-Phantolide, ADBI-Celestolide, and DPMI-Cashmeran) and the most prominent nitro musks (Musk Xylene-MX, and Musk Ketone-MK) in different wastewater treatment effluents in Canada and Sweden are presented to provide preliminary information on the variations within the emission pattern of these compounds. In all samples HHCB and AHTN were detected at concentrations of up to 1300 and 520 ngl(-1), respectively. ADBI, AHMI were also present, but close to the detection limit. The other PMF DPMI, ATTI, and more surprisingly musk ketone and musk xylene were not detected in any sample analysed. In comparison the samples from Canada were contaminated at a higher level than the Swedish samples, by a maximum factor of ca 10 for HHCB and AHTN.

Sediment contaminants and microtox toxicity tested in a direct contact exposure test

Limnic and brackish water sediments were tested in a modified contact exposure bioluminescence test, the Microtox test. A variety of chemical constituents were analyzed in the sediments such as metals, chlorinated pesticides, and polychlorinated biphenyls. Sulfur in the common elemental form and pore water hydrogen sulfide were also analyzed. The measured effect in the Microtox toxicity test was correlated with the various chemical parameters to determine the origin of the toxic effect. Based on multivariate data anlaysis, a group of metals including Cu, Zn, Pb, and Cd were correlated positively with the Microtox toxicity tested in the direct contact test. Similarly, but to a lesser extent sulfur, hydrogen sulfide, and the pesticides p,p′-DDT and p,p′-DDD were also correlated. Other pesticides and all the analyzed polychlorinated biphenyls were poorly, if at all, correlated with the toxicity of the samples. In a comparison with the Microtox toxicity of the pure compounds, it was found that, of the analyzed and tested compounds, Zn, Pb, Cu, and elemental sulfur were present in amounts high enough to produce an effect in the test system. This calculation was, however, based on the assumption (unrealistic) that the total amount of a compound in the sediment was available in the test. On the other hand, the metals Cd, Cr, and Ni were found at concentrations of a few percent or less of their EC50 concentrations in the Microtox test of the sediment, γ-Hexachlorocyclohexane and p,p′-DDT were also far less than the concentration required to give an effect in the test system. The pore water content of hydrogen sulfide was also too small to affect the test organism at the EC50 dilution and, similarly, the fraction of the toxicant in the remaining aqueous phase in the sediment after separation of the pore water. Thus only the three metals Zn, Pb, and Cu, and elemental sulfur, were found in concentrations that would give an effect in the test system (0.68–398 times the effect), provided that the substances were available for the organisms. Consequently, elemental sulfur, Zn, Pb, and Cu were indicated as causing the effect in the Microtox test of sediments and not a series of other metal ions, nor tested chloropesticides or chlorinated biphenyls.

DDT isomers and metabolites in the environment: an overview

It is known for decades that the isomeric composition of organic pollutants can be influenced substantially by environmental processes such as biotransformation or transfer between compartments. This accounts also for the pesticide 2,2,-bis(4-chlorophenyl)-1,1,1-trichloroethane, better known as p,p′-DDT, and its accompanied substitution isomer 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1,1-trichloroethane (o,p′-DDT). Although many studies followed the environmental fate of DDT, only very few publications reported on quantitative data of both o,p′- and p,p′-isomers. Therefore this condensed review describes evidence for remarkable changes and shifts in o,p′-/p,p′-ratios of DDT-related compounds. The application of isomer-specific analysis remains dominantly on emission source apportionment, for example, to differentiate DDT and dicofol emission. Only very few studies linked observed isomer shifts to aspects of environmental processes, such as (1) volatility from soil to air, (2) environmental stability in soil or (3) bioaccumulation in fishes. Additionally, several studies failed to use isomer-specific interpretation in order to obtain more detailed insight into environmental processes, for example, for observed isomer shifts during air–water fluxes. The o,p′-/p,p′-ratios of DDT and its main metabolite DDD have been detected more or less on the same level, whereas the isomers of the second main metabolite DDE were definitely depleted by the o,p′-isomer in all environmental compartments, indicating a general isomer-specific differentiation during DDT metabolism.

Non-target screening analysis of river water as compound-related base for monitoring measures

Background, aim, and scopeBuilding up a comprehensive accurate monitoring program requires the knowledge on the contamination in principal, complemented by detailed information on individual contaminants. The selection of pollutants to be considered in monitoring actions is based dominantly on the information available about their environmental relevance (e.g., persistence, bioaccumulation potential, toxicological and ecotoxicological properties) and their occurrence within the affected environmental system. Therefore, this study focused on the identification of organic contaminants in selected German and European rivers to demonstrate the usefulness of a screening approach as complementary base for the compound selection process within monitoring activities.Materials and methodsGas chromatography-mass spectrometry-based screening analyses were performed on five and six samples from German and European rivers, respectively. Identification of individual contaminants was based on the investigation of mass spectral and gas chromatographic properties compared with databases and reference materials.ResultsThis study summarized the results of non-target screening analyses applied to river water samples and focused dominantly on, so far, unnoticed organic contaminants. Numerous compounds have been identified belonging to the groups of pharmaceuticals, technical additives, pesticides, personal care products, and oxygen-, nitrogen-, and sulfur-containing compounds of obviously anthropogenic origin. They are discussed in terms of their structural properties, their possible application or usage, and the environmental information available so far.DiscussionGenerally, two different groups of compounds have been differentiated that might contribute to potential monitoring programs. Firstly, more specific contaminants characterizing the individual riverine systems have been depicted (e.g., 4-chloro-2-(trifluoromethyl)aniline, di-iso-propylurea). The consideration of these substances in monitoring analyses to be applied to the corresponding catchment areas is recommended in order to monitor the real state of pollution. Secondly, contaminants have been introduced that appeared with higher multiplicity throughout the different river systems (e.g., TMDD, TXIB). Since these compounds tend to obviously have an elevated environmental stability accompanied by a widespread distribution, it is recommended to consider them in international high-scale monitoring programs.ConclusionsFor monitoring purposes, a fundamental knowledge on the diversity of pollutants is an important precondition, which can be supported by screening analyses. Obviously, numerous organic contaminants have been neglected so far in environmental studies on river water, comprising also investigation on potential harmful effects and, therefore, their implementation in monitoring activities has been hindered.Recommendations and perspectivesTherefore, based on the results of this study, screening analyses should be established as principle tools to improve and complement the substance spectra for monitoring purposes. Secondly, scientific efforts should be strengthened to expand our knowledge on actually appearing organic contaminants in riverine systems.

PAH-profiles in sediment cores from the Baltic Sea

To document the historical input the PAH-profiles of sediment cores in two different basins of the Baltic Sea, the Gotland Basin (GB) and Arkona Basin (AB), were analysed by means of GC-MS. 35 PAHs were quantified in all samples, and additionally, several marker PAHs, like Cyclopenta[cd]phenanthrene (CCP) for combustion processes and retene for terrigenous input, were quantified in selected samples. The preindustrial sediments (older than 200-250 years) in the GB core illustrate concentrations <100 ng PAH15 g(-1) d.w. Calculated PAH-ratios indicated combustion processes as the main sources for both basins. The Perylene concentrations within the sediment cores decrease with increasing depth, along with an increase in relative percentage, indicating slow diagenetic processes. The preservation and enrichment of the introduced PAHs was more pronounced in the GB core.

Structural diversity of organochlorine compounds in groundwater affected by an industrial point source.

Groundwater samples contaminated by an industrial point source were analysed in order to reveal the structural diversity of halogenated organic contaminants. Particular focus was laid on the metabolites and derivatives related to the pesticides DDT (2,2-bis(chlorophenyl)-1,1,1-trichlorethane) and lindane (γ-hexachlorocyclohexane). Additionally, a wide range of chlorinated and brominated xenobiotics were identified. These results represent a high degree of contamination with organochlorine compounds illustrating a considerable structural diversity in groundwater in the vicinity of the industrial plant. The polar DDT-metabolite DDA (2,2-bis(chlorophenyl)acetic acid), which has been neglected in water studies widely, represents the main DDT metabolite analysed in the water samples. Besides DDA, some unknown substances with structural relation to DDA and DDT were detected and identified, in detail 2,2-bis(4-chlorophenyl)acetic acid N-methyl amide (DDAMA) and 2,2-bis(4-chlorophenyl)acetic acid n-butyl ester (DDABE). As an overall implication of this study it has to be demanded that analysis of industrially affected ground waters have to be based on screening analysis for a comprehensive view on the state of pollution.

Polycyclic aromatic compounds and microtox® acute toxicity in contaminated sediments in Sweden

Limnic and brackish aquatic sediments from contaminated locations in Sweden were analysed for polycyclic aromatic compounds (PACs) and tested for acute aquatic toxicity. The organic compounds were analysed in solvent-extractable and alkaline-treated fractions to complete the analysis of a set of priority pollutants according to the Swedish EPA. Additionally, the acute toxicity was measured by the solid phase Microtox test. The measured effects were correlated with sedimentological and chemical parameters. Analysis revealed no indication of a contribution of PACs to the acute sediment toxicity in highly contaminated sediments, with concentrations in the range of 11.3-307 μg SPAC37/39/g dry matter. Despite a high ranking of 3 to 5 within the Swedish EPA list for coastal sediments, the acute toxicity results indicate a very low bioavailability of the analysed PACs from the creosote and combustion-contaminated sediments. A correlation of acute toxicity to elemental sulfur was indicated.

Bleidner vapour phase extraction technique for the determination of organochlorine compounds in lake sediments.

SummaryThe vapour phase extraction technique according to Bleidner has been applied to the trace analysis of organochlorine pesticides and PCB in water sediments. This method eliminates time consuming drying, extracting, and clean-up steps in comparison with the conventional (Soxhlet) methods. The method developed is sufficiently sensitive and shows satisfying recovery results — with the exception of γ-HCH. Low yields of the DDT family are not caused by artifacts but are rather due to irreversible adsorption to sediment and fast metabolizing power of this substrate.