Reimer Herrmann

Chemodynamics, transport behaviour and treatment of phthalic acid esters in municipal landfill leachates

Large amounts of phthalic acid esters (PAEs) are leached from plastics dumped at municipal landfills. This leachate transports PAEs either adsorbed on particulate matter or in dissolved phase. Dissolved organic macromolecules, mainly humic-like substances, enhance the solubility of PAEs. In the biochemical environments of municipal landfills short chain PAEs can be degraded by base-catalyzed hydrolysis or by microorganisms which enzymatically split the side chains. However, there is no cleavage of the aromatic ring. Long chain PAEs like di-(2-ethylhexyl) phthalate are neither degraded abiotically nor by microorganisms. Hence, these PAEs can be leached and washed out of leaky landfills into the groundwater and thus continue to be a threat to the aquatic environment. Only a combined UV radiation/ozonation treatment is capable of fully destroying PAEs.

TRANSPORT OF POLYCYCLIC AROMATIC HYDROCARBONS THROUGH A PARTLY URBANIZED RIVER BASIN

The PAH-pollutant loads resulting from storm runoff to a receiving stream are associated with high concentrations of suspended sediments. This is explained by the sorption coefficients and isotherms on street dust, suspended solids, bedload and other sorbents. Pollutographs for a stream with storm runoff mainly from storm water overflows from a combined sewered medium sized town show strong ‘first-flush’ phenomena. Rainfall and bedload contribute only to a lesser extent to the overall transport which stems from street dust washoff. High correlation between total PAH load and maximum flow, but no relation between total PAH load and the number of days since the previous storm, indicates a ‘low washoff case’ under ‘transport limited’ conditions. 3.4-Benzopyrene load was modeled by a pollutant washoff function analoguous to that of the EPA storm water model.

Development and validation of a method for determination of trace levels of alkylphenols and bisphenol A in atmospheric samples.

A method has been developed and validated in order to assess the occurrence of the alkylphenols tert-octylphenol and the isomers of technical nonylphenol as well as bisphenol A in gasphase and aerosol samples of a remote area. Gasphase samples were adsorbed to XAD2 resin, aerosol samples were taken on glass fiber filters. After ultrasonic extraction, clean-up by column chromatography and silylation of the analytes, ten nonylphenol peaks were quantified separately using a GC-MSD-SIM method. The absolute limits of detection and determination are in the range of a few pg per compound, which is a prerequisite for the quantification of the analytes in relatively unpolluted air. The precision of the whole analytical method is in the range of 1-17% and the recoveries range from 57% to 80%. Problems were encountered during method development due to the tendency of the analytes to sorb to glass surfaces. Silanisation of glassware was crucial to achieve acceptable recoveries. The widespread use of the analytes in plastic resins resulted in sample contamination. For this reason a careful choice of sampling material was necessary. Measured concentrations in gasphase samples (lower nanogram per m3 range) and aerosol samples (upper picogram per m3 range) are one to three orders of magnitude below already published concentrations.

Analysis of cationic surfactants by microbore high-performance liquid chromatography-electrospray mass spectrometry.

In the work reported here, a state-of-the-art analytical method for the quantitative analysis of cationic surfactants in environmental matrixes is described. High-performance liquid chromatography on-line coupled via an electrospray interface to a mass spectrometer (HPLC-ESP-MS) is used for the determination of ditallowdimethylammonium chloride (DTDMAC) and two of its most important substitution products, diethylester dimethylammonium chloride (DEEDMAC) and Diesterquaternary (DEQ). Using the analytical method developed in our laboratory, it is possible to determine single homologues of these surfactants as well as the first hydrolysis products of DEQ and DEEDMAC. In combination with our extraction procedure, which is based on ion-pair extraction, cationic surfactants were determined in environmental samples (sewage influent, sewage effluent, river water); concentrations ranged from 0.4 to 140 μg/L. The linear dynamic range of the HPLC-ESP-MS method, which is an injected amount between 0.4 and 30 ng, is well suitable for the analysis of these samples, as well as the performance of the quantification through external standards.

The behavior of hydrophobic, organic micropollutants in different Karst water systems

During and after the melting of snow, Karst groundwater of an agriculturally used and a wooded catchment area situated on a Dolomite plateau in Upper Franconia (F.R.G.) were investigated. Seventeen hydrochemical and hydraulic parameters were analyzed in the Karst water of two different springs in the course of the snow melting. Hydrograph analysis and the temporal variation of chloride concentrations were used to distinguish different types of Karst waters reaching the spring. Polycyclic aromatic hydrocarbons (benzo(a)pyrene, fluoranthene, benzo(ghi)perylene) and chlorinated pesticides (α-BHC, lindane) are transported in Karst waters adsorbed on suspended solids, dissolved in water and adsorbed on dissolved humic material. Most of the organic contaminants reach the groundwater level with conduit and trickle water. However, BHC-molecules also arrive at the spring with seepage water three weeks after the meltwater input. Using Karst springs as natural lysimeters for their catchment areas, pollutant input-output balances were calculated for PAHs and BHCs revealing that 87.5 to 99.7% of the atmospheric micropollutants released from the snow cover are retained in the Karst system. Potential pollutant sinks are proposed and discussed.

Tracing faecal pollution by coprostanol and intestinal bacteria in an ice-covered finnish lake loaded with both industrial and domestic sewage

The relationships existing between coprostanol (5β-cholestan-3β-ol), faecal indicator bacteria and various physico-chemical tracer and bacterial stress factors in an ice-covered Finnish lake were investigated. Field observations show that coprostanol lies below the theoretical mixing line, indicating a net removal, primarily by settling together with suspended sediments. Faecal indicator bacteria, however, are differently transported and are removed by various environmental factors e.g. industrial wastes. Thus, only faecal streptococci show a regional covariance to coprostanol. Principal component analyses reveal a strong correlation between coprostanol and faecal streptococci in water but not with coliforms and sulfite reducing sporing anaerobs. However, in sediments also coliforms are correlated significantly with coprostanol and faecal streptococci.Therefore it might be necessary to estimate the quality of those waters polluted by both industrial and faecal wastes by means of coprostanol, a principal sterol in sewage of man and higher animals, which is thus well suited as a chemical marker of faecal pollution.

Regional patterns of contaminants (PAH, pesticides and trace metals) in snow of Northeast Bavaria and their relationship to human influence and orographic effects

In January 1978, 31 snow samples were collected throughout NE-Bavaria and were analyzed for trace metals (Zn, Pb, Cd, Cu), pesticides (α-BHC, Lindane, Aldrin, Dieldrin) and polycyclic aromatic hydrocarbons (PAH) (3,4-benzopyrene, 1,12-benzoperylene, fluoranthene and 3,4-(o-phenylene)-pyrene). The regional pattern of PAH-concentrations can be explained as follows: above urban areas and through orographic uplifting of the air, PAHs are scavenged from the atmosphere by snow. The trace metals and specific conductance show similar regional patterns, although the pattern for Pb is influenced by automobile traffic as well as by glass and ceramic industries. The pesticides show less distinct patterns relative to the other two groups of contaminants. Using multivariate statistics it was shown that the trace metals with the exception of Pb and the PAHs had regional patterns similar to each other but distinct from the pesticides. Although orography, urbanization and industries are shown to affect the regional patterns of PAHs and the trace metals, this is not the case for pesticides. They originate from diffuse sources in agricultural and f forested lands.

Regional patterns of polycyclic aromatic hydrocarbons in NE-Bavarian snow and their relationships to anthropogenic influence and air flow

Summary The regional patterns of PAH-concentrations in NE-Bavarian snow may be explained as follows: snow scavenges PAH over urban centres and orographic uplifting of air over mountains increases the scavenging by snow. By multivariate statistical analysis it could be shown that the influence of heating on the PAH-concentrations in snow is stronger than that of combustion by traffic. As all PAH load only one single principal component, a constant qualitative PAH pattern is evident. This allows to reduce the measurements of PAH to only one for each sample.

Pesticide residues in biological waste

The aim of this study was to detect crop protection products (CPP) in single fractions of biological waste and to estimate pesticide concentrations in biological waste, depending on its composition. The composition of biological waste was determined from the literature, which provided information on its local and seasonal variability. The residue analysis included 17 pesticides for the analysis of tropical fruit peels and 48 pesticides for other fractions, e.g. vegetables, other fruits and ornamental flowers. The freeze-dried samples were extracted ultrasonically and purified by means of gel permeation chromatography. The analysis was carried out using gas chromatography with a mass selective detector in the selected ion monitoring mode. All tropical fruit peels contained CPP-residues. Thiabendazole was the most important contaminant with respect to the concentration and frequency of occurrence. The vegetables, other fruits and flowers also contained CPP-residues, such as the fungicides captan and dodemorph and the insecticide endosulfan. Based on import data and the composition of biological waste, the CPP-content of biological waste was estimated for rural and urban areas in summer and winter. Due to the higher percentage of tropical fruit peels, thiabendazole was the main contaminant in winter. The total concentration of CPP, summed up over all substances, ranged between 828 and 1829 microg(kg ww)(-1).

Comparing the effects of acidic deposition on the chemistry of small streams in the South Island of New Zealand with those in the Fichtelgebirge, F.R.G.

Summary There are some major differences in the chemical composition of unpolluted clear and brownwater (natural acid) streams in NZ and the polluted White Main in Bavaria, FRG. Sulfate concentrations are 10–20 times higher in the White Main and atmospheric inputs of strong acids (H 2 SO 4 and HNO 3 ) cause pH values about 5.0 and lower. Clearwaters in NZ show neutral pH values of between pH 6.6–8.0 whereas brownwaters have a pH of around 4.0, but their acidity is derived from organic acids. Concentrations of A1 were low in the NZ clearwaters and consist mainly of polymeric species. Bownwaters show relatively high a1 concentrations, dominated by monomeric A1 species, but these are mostly complexed with organic acids. In contrast to this, the White Main has high concentrations of the toxic monomeric inorganic form.