Monitoring of waste deposit derived groundwater contamination with organic tracers

Specific anthropogenic substances derived from seepage and leakage water from a waste deposit landfill were analysed in groundwater and drainage effluents using gas chromatography-mass spectrometry (GC/MS). Here, we demonstrate the application of an organic marker approach to study lateral and vertical distribution of contamination as well as the long-term emission behaviour. Source-specific and environmentally-stable pesticides, plasticisers and pharmaceuticals, such as N,N-diethyl toluamide, N-butyl benzene sulfonamide, clofibric acid, mecoprop and bisphenol A, were quantitatively analysed. A distinct lateral expansion was detected. Although temporal variations were high, no significant trend was observed.     

Inter- and intra-species variation in acute zinc tolerance of field-collected cladoceran populations

Acute zinc toxicity was assessed for 10 freshwater cladoceran species collected in six different ecosystems across Europe and for two standard laboratory-reared species (Daphnia magna and Ceriodaphnia dubia). The collected organisms belonged to five different genera: Daphnia (subgenus Daphnia and Ctenodaphnia), Ceriodaphnia, Simocephalus, Acroperus and Chydorus. The 48-h EC50 of the field-collected organisms tested in standard laboratory water ranged from 375+/-141 to 4314+/-1513 microg Znl(-1). The laboratory clone of D. magna was less sensitive than the majority of the field-collected species, while our laboratory Ceriodaphnia dubia was the second most sensitive. Considerable inter-species variation was found within the genus of Ceriodaphnia (factor 6) and within the genus Daphnia (factor 8). Among the different (sub)genera tested, Chydorus and Ctenodaphnia were significantly more tolerant than the others (up to a factor 3 difference). A significant positive relationship (r2=0.67, p<0.05) between the mean cladoceran 48-h EC50 and the ambient zinc concentration of the different aquatic systems was demonstrated, suggesting a role of acclimation and/or adaptation. No significant correlation between the acute zinc tolerance and the length of the organisms was found.     

Levels and pattern of volatile organic nitrates and halocarbons in the air at Neumayer Station (70 degrees S), Antarctic

Levels and patterns of C1-C4/C9 organic nitrates were measured for the first time in Antarctica. The sampling was done by adsorptive enrichment on Tenax TA followed by thermodesorption cold-trap high resolution capillary gas chromatography with electron capture detection. 2-70 1 air on-column have been analyzed this way. C1-C9 alkyl mononitrates, C2-C4 alkyl dinitrates, C2-C4 hydroxy alkyl nitrates, and halocarbons could be identified in air samples collected near the German Neumayer Research Station, Antarctica, in February 1999. Volatile biogenic and anthropogenic halocarbons were used to assess the origin of the air parcels analyzed. The average concentration measured for sigmaC2-C6 alkyl nitrates was in the range of 9.2 +/- 1.8 ppt(v), while the sum of the mixing ratios of six C2-C4 hydroxy alkyl nitrates was in the range of 1.1 +/- 0.2 ppt(v). Moreover, C2-C4 alkyl dinitrates were found at levels near the detection limit of 0.1-0.5 ppt(v). The concentrations of organic nitrates found in Antarctic air represent ultimate baseline levels due to chemical and physical loss processes during long-range transport in the air. The South Atlantic and the Antarctic Ocean as a general secondary source for organic nitrates in terms of an air/sea exchange equilibrium has to be evaluated yet, but it seems logical. Our results confirm the common assumption that there are no biogenic marine sources of C2-C9 organonitrates. We have found a level of > 80 ppt(v) for methyl nitrate. This level if it can be confirmed in a systematic survey requires a strong biogenic source of methyl nitrate in the Antarctic Ocean.     

(M)VOC and composting facilities. Part 2: (M)VOC dispersal in the environment

BACKGROUND, AIMS AND SCOPE: Composting facilities are known to release odorous volatiles due to biodegradation of municipal waste and plant residues. Although odour perception and its grading is influenced by experience, attitude and adaptation, these emissions have created a lack of acceptance for residents in the vicinity of composting facilities. Enclosure of compost pile halls, ventilation systems and biofilters are often insufficient to minimise the burden of compost-derived compounds in the air. Moreover, economic considerations forced smaller communities to establish less sophisticated facilities with open storage areas and other relevant sources for wind-borne dispersal of bioaerosols. Aim of the present study was to characterise the immission and dispersal of microbial volatiles (MVOC) and, besides, to find coincidences between MVOC and compost odour. METHODS: In the course of this study, the surroundings of two composting facilities, differing in their type of process engineering, were investigated for emission of volatiles in the environment. Both microbially and plant-derived substances were assessed, several of which have low odour thresholds. Air samples were taken in distances ranging from 50 to 800 m in a downwind direction from each facility. RESULTS AND DISCUSSION: Compost-derived and microbial volatile organic compounds (MVOC) were found at distances of up to 800 m from the composting facilities. Terpenes like alpha-pinene, camphene and camphor were the dominant compounds and coincided with typical compost odour, whereas several typical MVOC were not found at greater distances. The terpenes in combination with certain MVOC may play an important role in the perception of compost odour. Exposure concentrations were not of toxicological relevance, but sensory irritation and psychohygienic effects due to an annoyance potential of such compounds should not be dismissed. RECOMMENDATIONS AND OUTLOOK: Although terpenes are generally associated with pleasant odour characteristics, they seemed to contribute to malodours in a mixture with other VOC, in this context of volatile waste from compost facilities. Malodorous emissions from biowaste have to be considered as sources of health complaints and the investigation of mixtures of compost-derived volatiles is still inevitable. Exposure levels have to be discussed taking VOC mixtures into account. Within composting facilities, technical devices have to be improved to minimise dispersal of volatiles to prevent residents from immissions eventually causing health complaints.     

Influence of ageing on zinc bioavailability in soils

Currently, soil quality criteria or soil risk assessments of metals are based on laboratory toxicity tests which are carried out in soils freshly spiked with metal salts. With these data, species sensitivity distributions are fitted, from which hazardous concentrations and predicted no effect concentrations are derived. However, due to long-term processes, called ageing, soil metal availability decreases with time. Here we show that pH is the most important parameter determining the effect of ageing on zinc partitioning in soils, with the effect of ageing becoming more important with increasing pH. Furthermore, zinc bioavailability, expressed as the internal zinc concentrations in red clover (Trifolium pratense) is closely related to pore water zinc concentration. In addition, there is a clear dose-response relationship between the survival of the earthworm Eisenia fetida and the calcium chloride-extracted zinc fraction. These results indicate that zinc partitioning can be used to predict zinc bioavailability to terrestrial organisms. However, the use of spiked soils in toxicity assays can result in an over-estimation of the effects of zinc, especially at a high pH.     

Enhanced experimental flexibility and control in ecotoxicological mesocosm experiments--a new outdoor and indoor pond and stream system

Scope The German Federal Environmental Agency has put into operation a new modular mesocosm system consisting of eight outdoor and eight indoor ponds and streams in order to investigate fate and effects of chemicals and municipal wastewater in aquatic ecosystems. General design and special characteristics are given to demonstrate the wide range of possibilities for experimental research. - General design. Each of the 16 streams with riffle and pool sections can be varied in length up to 106 m. The streams can be run as circular or flow-through systems at a flow velocity of 0.02 to 0.6 m/s. Physico-chemical standard parameters are measured on-line. The 16 ponds, which can be connected to the stream systems, are equipped with drainage and pore water-sampling devices for simulating processes in the littoral zone including influent and effluent ground water flow. Perspectives Since the highly flexible and controllable construction also allows treating a wide range of hydrological and ecological experiments external institutions are invited to submit proposals.     

Mercury pollution and macrophage centres in pike (Esox lucius) tissues

From June 1993 to October 1994, studies have been carried out on the effects of mercury in the Oder River and pike tissue contamination (muscle, kidney, liver). The mean mercury contents in the sediment range from 0.03 to 1.1 mg/kg dry weight. In the pike muscle, between 0.22 and 0.85 mg/kg, on a wet weight basis, were found. The measured mercury concentrations were analysed in relation to the number of macrophage centres of the liver, spleen and kidney of the pike. Positive correlations between mercury and MC response (0.54 ≤ r ≤ 0.79, p < 0.05) were found in all of these organs. The suitability of the macrophage-centre-response as a possible bioindicator for mercury pollution is discussed in the literature. In our study, the response of MCs was found to be suitable as a biomarker for the impairment of fish health.     

A qualitative sampling method for monitoring water quality in temporary channels or point sources and its application to pesticide contamination

A water-sampling device to monitor the quality of water periodically and temporarily flowing out of concrete tubes, sewers or channels is described. It inexpensively and easily enables a qualitative characterization of contamination via these point-source entry routes. The water sampler can be reverse engineered with different sizes and materials, once installed needs no maintenance, passively samples the first surge, and the emptying procedure is short. In an agricultural catchment area in Germany we monitored an emergency overflow of a sewage sewer, an outlet of a rainwater sewer and two small drainage channels as input sources to a small stream. Seven inflow events were analysed for 20 pesticide agents (insecticides, fungicides and herbicides). All three entry routes were remarkably contaminated. We found parathion-ethyl concentrations of 0.3 microg l(-1), diuron up to 17.3 microg l(-1), ethofumesate up to 51.1 microg l(-1), metamitron up to 92 microg l(-1) and prosulfocarb up to 130 microg l(-1).     

Competing TCE and cis-DCE degradation kinetics by zero-valent iron-experimental results and numerical simulation

The successful dechlorination of mixtures of chlorinated hydrocarbons with zero-valent metals requires information concerning the kinetics of simultaneous degradation of different contaminants. This includes intraspecies competitive effects (loading of the reactive iron surface by a single contaminant) as well as interspecies competition of several contaminants for the reactive sites available. In columns packed with zero-valent iron, the degradation behaviour of trichloroethylene (TCE), cis-dichloroethylene (DCE) and mixtures of both was measured in order to investigate interspecies competition. Although a decreasing rate of dechlorination is to be expected, when several degradable substances compete for the reactive sites on the iron surface, TCE degradation is nearly unaffected by the presence of cis-DCE. In contrast, cis-DCE degradation rates decrease significantly when TCE is added. A new modelling approach is developed in order to identify and quantify the observed competitive effects. The numerical model TBC (Transport, Biochemistry and Chemistry, Sch?fer et al., 1998a) is used to describe adsorption, desorption and dechlorination in a mechanistic way. Adsorption and degradation of a contaminant based on a limited number of reactive sites leads to a combined zero- and first-order degradation kinetics for high and low concentrations, respectively. The adsorption of several contaminants with different sorption parameters to a limited reactive surface causes interspecies competition. The reaction scheme and the parameters required are successfully transferred from Arnold and Roberts (2000b) to the model TBC. The degradation behaviour of the mixed contamination observed in the column experiments can be related to the adsorption properties of TCE and cis-DCE. By predicting the degradation of the single substances TCE and cis-DCE as well as mixtures of both, the calibrated model is used to investigate the effects of interspecies competition on the design of permeable reactive iron barriers. Even if TCE is present in only small concentrations (>3% of molar cis-DCE concentration) it is the contaminant limiting the residence time and the required thickness of the iron barrier.     

Copper regulation and homeostasis of Daphnia magna and Pseudokirchneriella subcapitata: influence of acclimation

This study aimed to evaluate (1) the capacity of the green alga Pseudokirchneriella subcapitata and the waterflea Daphnia magna to regulate copper when exposed to environmentally realistic copper concentrations and (2) the influence of multi-generation acclimation to these copper concentrations on copper bioaccumulation and homeostasis. Based on bioconcentration factors, active copper regulation was observed in algae up to 5 microg Cu L(-1) and in daphnids up to 35 mug Cu L(-1). Constant body copper concentrations (13+/-4 microg Cu g DW(-1)) were observed in algae exposed to 1 through 5 microg Cu L(-1) and in daphnids exposed to 1 through 12 microg Cu L(-1). At higher exposure concentrations, there was an increase in internal body copper concentration, while no increase was observed in bioconcentration factors, suggesting the presence of a storage mechanism. At copper concentrations of 100 microg Cu L(-1) (P. subcapitata) and 150 microg Cu L(-1) (D. magna), the significant increases observed in body copper concentrations and in bioconcentration factors may be related to a failure of this regulation mechanism. For both organisms, internal body copper concentrations lower than 13 microg Cu g DW(-1) may result in copper deficiency. For P. subcapitata acclimated to 0.5 and 100 microg Cu L(-1), body copper concentrations ranged (mean+/-standard deviation) between 5+/-2 microg Cu g DW(-1) and 1300+/-197 microg Cu g DW(-1), respectively. For D. magna, this value ranged between 9+/-2 microg Cu g DW(-1) and 175+/-17 microg Cu g DW(-1) for daphnids acclimated to 0.5 and 150 microg Cu L(-1). Multi-generation acclimation to copper concentrations >or =12 microg Cu L(-1) resulted in a decrease (up to 40%) in body copper concentrations for both organisms compared to the body copper concentration of the first generation. It can be concluded that there is an indication that P. subcapitata and D. magna can regulate their whole body copper concentration to maintain copper homeostasis within their optimal copper range and acclimation enhances these mechanisms.