Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in breast milk of first-time Irish mothers: impact of the 2008 dioxin incident in Ireland

The 2008 dioxin incident in Ireland resulted in elevated concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in Irish pork and pork products, due to the consumption of contaminated animal feed by pigs. In order to investigate any resulting impact on the Irish population, these contaminants were measured in pooled breast milk samples from 109 first-time mothers, collected in 2010. A comparison of the results with similar data from 2002 revealed generally lower concentrations of PCDD/Fs and dioxin-like PCBs in the 2010 samples, confirming the declining trend reported by many authors. Contaminant concentration levels for both 2002 and 2010 were generally slightly lower than those reported internationally, with a mean combined PCDD/F and PCB WHO-TEQ of 9.66 pg g⁻¹ fat, for an overall pooled sample of milk from 2010. An apparent slight increase in PCDFs was observed between 2002 and 2010 (from 2.73 pg WHO-TEQ g⁻¹ fat to 3.21 pg WHO-TEQ g⁻¹ fat), with the main contributory congener being 2,3,4,7,8-PentaCDF. While it cannot be totally discounted that the slight increase in 2,3,4,7,8-PentaCDF and in the overall PCDF WHO-TEQ in breast milk could be attributable to consumption of Irish pork during the 2008 incident, we consider that it is more likely that this was due to other factors, including the predominantly urban/industrial sampling locations for the 2010 samples, compared to 2002.     

Ecological scenarios analyzed and evaluated by a shallow lake model

We applied the complex ecosystem model EMMO, which was adopted to the shallow lake Müggelsee (Germany), in order to evaluate a large set of ecological scenarios. By means of EMMO, 33 scenarios and 17 indicators were defined to characterize their effects on the lake ecosystem. The indicators were based on model outputs of EMMO and can be separated into biological indicators, such as chlorophyll-a and cyanobacteria, and hydro-chemical indicators, such as phosphorus. The question to be solved was, what is the ranking of the scenarios based on their characterization by these 17 indicators? And how can we handle high quantities of complex data within evaluation procedures? The scenario evaluation was performed by partial order theory which, however, did not provide a clear result. By subsequently applying the hierarchical cluster analysis (complete linkage) it was possible to reduce the data matrix to indicator and scenario representatives. Even though this step implies losses of information, it simplifies the application of partial order theory and the post processing by METEOR. METEOR is derived from partial order theory and allows the stepwise aggregation of indicators, which subsequently leads to a distinct and clear decision. In the final evaluation result the best scenario was the one which defines a minimum nutrient input and no phosphorus release from the sediment while the worst scenario is characterized by a maximum nutrient input and extensive phosphorus release from the sediment. The reasonable and comprehensive results show that the combination of partial order, cluster analysis and METEOR can handle big amounts of data in a very clear and transparent way, and therefore is ideal in the context of complex ecosystem models, like that we applied.     

Mixing-controlled biodegradation in a toluene plume--results from two-dimensional laboratory experiments

Various abiotic and biotic processes such as sorption, dilution, and degradation are known to affect the fate of organic contaminants, such as petroleum hydrocarbons in saturated porous media. Reactive transport modeling of such plumes indicates that the biodegradation of organic pollutants is, in many cases, controlled by mixing and therefore occurs locally at the plume's fringes, where electron donors and electron-acceptors mix. Herein, we aim to test whether this hypothesis can be verified by experimental results obtained from aerobic and anaerobic degradation experiments in two-dimensional sediment microcosms. Toluene was selected as a model compound for oxidizable contaminants. The two-dimensional microcosm was filled with quartz sand and operated under controlled flow conditions simulating a contaminant plume in otherwise uncontaminated groundwater. Aerobic degradation of toluene by Pseudomonas putida mt-2 reduced a continuous 8.7 mg L(-1) toluene concentration by 35% over a transport distance of 78 cm in 15.5 h. In comparison, under similar conditions Aromatoleum aromaticum strain EbN1 degraded 98% of the toluene infiltrated using nitrate (68.5+/-6.2 mg L(-1)) as electron acceptor. A major part of the biodegradation activity was located at the plume fringes and the slope of the electron-acceptor gradient was steeper during periods of active biodegradation. The distribution of toluene and the significant overlap of nitrate at the plume's fringe indicate that biokinetic and/or microscale transport processes may constitute additional limiting factors. Experimental data is corroborated with results from a reactive transport model using double Monod kinetics. The outcome of the study shows that in order to simulate degradation in contaminant plumes, detailed data sets are required to test the applicability of models. These will have to deal with the incorporation of existing parameters coding for substrate conversion kinetics and microbial growth.     

Initial Changes in Refilled Lysimeters Built with Metal Polluted Topsoil and Acidic or Calcareous Subsoils as Indicated by Changes in Drainage Water Composition

Soil translocation for recultivation of soil removed from construction sites and for the preparation of refilled lysimeters inevitably involves disturbance of soil structure, and, if intermediate storage is included, also drying and rewetting of the soil. We report on an experiment with model forest ecosystems, where uncontaminated forest subsoils were covered with non-contaminated or freshly heavy metal (mainly Zn and Cu) contaminated topsoil in large lysimeters. Monitoring of the chemical composition of the drainage water revealed two distinct soil conditioning phases. During an initial phase of about a year strongly elevated nitrate and sulfate concentrations occurred that were attributed to a mineralisation flush caused by the increased accessability of mineralisable nitrogen and sulfur in destroyed aggregates. These effects were significantly larger in lysimeters with calcareous subsoil than in those with acidic subsoil. The second phase was characterised by a gradual decrease in dissolved organic carbon and sulfate concentrations, in particular in the acidic subsoil. This decrease may be attributed to the depletion of pools made accessible during aggregate destruction or the formation of new aggregates. These chemical changes had only little effects on the concentrations of copper and zinc in the drainage water. Based on our results, it can be concluded that large refilled lysimeters can be used for many purposes without risk of compromised results, if a conditioning phase of about 1 year with sufficiently moist soil conditions is respected. Nevertheless, gradual changes in soil chemical characteristics still occur after this initial phase. Implications for the recultivation of sites using relocated soils are discussed.     

Chemisch-analytische Untersuchung von Arsenkampfstoffen und ihren Metaboliten

Arsenic containing chemical warfare agents (cwa) are persistent in the environment and continue to contaminte soil and ground water. In this paper the chemical rections of the cwa diphenylarsine chloride (CLARK I), phenylarsine dichloride (PFIFFIKUS), ethylarsine dichloride (DICK) and of chlorovinyl arsenic compounds (LEWISITE) are shown. The posibilities of the detection and determination of this cwa and their metabolites are presented.     

Passivsammler zur Wasseruntersuchung

The topography and motion of contaminant plumes in groundwater may be determined by surveying the three-dimensional distribution of contaminant freights [1] as well as through a period-integral monitoring by contaminant dosimeters [1]. Conventional methods of taking water samples for chemical analysis cannot fulfill any of these requirements. Sorption active passive collectors suitable for corresponding surveys in gaseous phases are unsuitable for examination in aquifers. Passive collectors for the examination of undisturbed aquifers represent the central part of a probing device system developed by the authors for monitoring chemical and hydraulic parameters within all kinds of aquifers. These passive collectors permit both a determination of the relative contaminant freights at deliberate vertical spacing of vertically ordered measuring points, and period-integrating detection of vertical profiles of relative contaminant freights. The easy-to-handle passive collectors are suitable for the collection of organic and inorganic contaminants and may be evaluated by standardized chemical analysis methods. In this way, passive collectors fulfill the essential prerequisites for purpose-oriented monitoring of contaminant plumes. Moreover, passive collectors for ground water monitoring are well suited for the in situ-examination of any other aquifer, both still and fluent, regardless of its depth or extent. Examples of application may be sewage ducts, sewage plants, rivers, lakes, oceans, water samples and especially the identification of contaminants and trace substances.     

Application of microbial hot spots enhances pesticide degradation in soils

Through transfer of an active, isoproturon degrading microbial community, pesticide mineralization could be successfully enhanced in various soils under laboratory and outdoor conditions. The microbes, extracted from a soil having high native ability to mineralize this chemical, were established on expanded clay particles and distributed to various soils in the form of microbial "hot spots". Both, diffusion controlled isoproturon mass flow towards these "hot spots" (6microg d(-1)) as well as microbial ability to mineralize the herbicide (approximately 5microg d(-1)) were identified as the main processes enabling a multiple augmentation of the native isoproturon mineralization even in soils with heavy metal contamination. Soil pH-value appears to exert an important effect on the sustainability of this process.     

PCDD/Fs and PCBs in butter samples from new European Union member states and a candidate country: analytical quality control, results and certain PCB-specific aspects

Milk and milk products have shown to be good indicator samples for the contamination of persistent organic pollutants (POPs) along the food chain. To gather information on whether exposure to dioxins and PCBs might cause a problem in countries about to join the European Union in 2004 or later, a study for evaluation of dioxin and levels of PCBs in 16 butter samples from eight countries (Cyprus, Czech Republic, Estonia, Lithuania, Poland, Romania, Slovenia and Slovakia) was performed. Comprehensive quality assurance/quality control (QA/QC) was requested. For this, eight quality control samples were included (in comparison to long-term mean, mean recovery for WHO-PCDD/F-TEQ of 97.9% with a CV of 3.0%, mean recovery for WHO-PCB-TEQ of 100.4% with a CV of 3.3%). Additionally, all butter samples were run as duplicates resulting in a confidence region of 95% statistical certainty of 4.6% for WHO-PCDD/F-TEQ and of 3.5% for WHO-PCB-TEQ. All samples except one from Romania were in the range of 0.21-0.59 pg WHO-PCDD/F-TEQ/g fat (upper bound), all samples except one from Romania and one from Estonia in the range of 0.32-0.82 pg WHO-PCB-TEQ/g fat (upper bound) and all samples except one from Romania and one from Estonia in the range of 0.57-1.23 pg sum WHO-TEQ/g fat (upper bound). The maximum values were found in samples from Romania (0.98 pg WHO-PCDD/F-TEQ/g fat; 1.75 pg WHO-PCB-TEQ/g fat) and Estonia (0.26 pg WHO-PCDD/F-TEQ/g fat; 1.62 pg WHO-PCB-TEQ/g fat). As a conclusion, all samples except one from Romania and one from Estonia were in the range of the actual low background contamination for PCDD/F and dioxin-like PCBs. The samples with elevated concentrations were below the EU action and maximum levels which have been valid since 2002, or will be applied from November 2006. In all samples except in one from Estonia, the contribution of dioxin-like PCBs to sum WHO-TEQ was 47-68% which reflects the usual range in Europe. In one sample from Estonia this contribution was 86% which points to a particular yet unknown PCB source. Thirty eight PCB congeners were determined allowing a detailed discussion of the relative contribution of individual congeners to the total PCB concentration. Correlation between PCB 153 and WHO-PCB-TEQ varied considerably between samples from different countries. Major tetra- or pentachlorinated mono-ortho PCBs without assigned TEFs were PCBs 60, 66, 74, and 110.     

Vertical profile of PCDD/Fs, dioxin-like PCBs, other PCBs, PAHs, chlorobenzenes, DDX, HCHs, organotin compounds and chlorinated ethers in dated sediment/soil cores from flood-plains of the river Elbe, Germany

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other organic micropollutants were determined in dated sediment/soil cores collected from the flood-plain of the river Elbe near Pevestorf (PT), approximately 125 km upstream of Hamburg, and Heuckenlock (HL) in southeast of Hamburg. Concentrations of PCDD/Fs peaked sharply at PT in the 1950s and at HL at the end of the 1940s. Cluster analyses provide evidence that the region of Bitterfeld-Wolfen (about 350-400 km upstream of Hamburg) could be the source of the PCDD/F contamination existing in the cores PT and HL since the 1940s. Obviously it is caused by sediments of the river Elbe of a similar composition. Whereas the PCDD/Fs, HCHs (hexacyclohexane isomers), DDX (DDT, DDD, DDE), and tetrachlorinated ethers in PT and HL presumably originated predominantly from the Bitterfeld-Wolfen region, organotin compounds in HL and dichlorinated haloethers in HL during the 1940s and 1950s can probably largely be attributed to emissions from the Hamburg region. Although they are separated by a large distance, in both sediment cores PT and HL concentrations and composition patterns of most organic micropollutants analyzed widely match. Inductively it can be concluded that similar contaminations will be found in many of the river bank soils between the Bitterfeld-Wolfen region and Hamburg. Excavation of top soils may uncover highly contaminated materials. Since the dated sediment cores show the variation in contaminants in the Elbe sediments over a defined time period, it is possible to make an approximate assessment of the actual degree of contamination to be expected in areas where in previous decades contaminated dredged sediments from the Elbe and from the Port of Hamburg have been deposited on land and used for building plots or for agricultural purposes.