Biological Activity in a Heavily Organohalogen-Contaminated River Sediment (8 pp)

Background, Aims and Scope Sediments of the Spittelwasser creek are highly polluted with organic compounds and heavy metals due to the discharge of untreated waste waters from the industrial region of Bitterfeld-Wolfen, Germany over the course of more than one century. However, relatively few data have been published about the chloroorganic contamination of the sediment. This paper reports on the content of different (chloro)organic compounds with special emphasis on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), and chlorobenzenes. Existing concepts for the remediation of Spittelwasser sediment include the investigation of natural attenuation processes, which largely depend on the presence of an intact microbial food web. In order to gain more insight in terms of biological activity, we analyzed the capacity of sediment microflora to degrade organic matter by measuring the activities of extracellular hydrolytic enzymes involved in the biogeochemical cycling of carbon, nitrogen, phosphorus and sulfur. Furthermore, the detection of physiologically active bacteria in the sediment, particularly of those known for their capability to reductively dehalogenate organochlorine compounds, illustrates the potential for intrinsic bioremediation processes. Methods PCDD/F and chlorobenzenes were analyzed by gas chromatography(GC)/mass spectrometry and GC/flame ionization detection, respectively. The activities of hydrolytic enzymes were determined from freshly sampled sediment layers using 4-methylumbelliferyl (MUF) or 7-amino-4-methylcoumarin-conjugated model compounds and kinetic fluorescence measurements. Physiologically active bacteria from different sediment layers were microscopically visualized by fluorescence in situ hybridization (FISH). Specific bacteria were identified by 16S rRNA gene amplification and sequencing. Results and Discussion The PCDD/F congener profile was dominated by dibenzofurans. In addition, the presence of specific tetra and pentachlorinated dibenzofurans supported the assumption that extensive magnesium production was one possible source for the high contamination. A range of other chloroorganic compounds, including several isomers of chlorobenzenes, hexachlorocyclohexane and 1,1,1-trichloro-2,2-bis (p-chloro-phenyl)ethane (DDT), was present in the sediment. Activities of extracellular hydrolytic enzymes showed a strong decrease in those sediment layers that were characterized by high contents of absorbable organic halogen (AOX), indicating disturbed organic matter decay. Interestingly, an abnormal increase of cellulolytic enzyme activities below the organochlorine-rich layers was observed, possibly caused by residual cellulose from discharges of sulfite pulping wastes. FISH revealed physiologically active bacteria in most sediment layers from the surface down to the depth of about 60 cm, including members of Desulfitobacterium (D.) and Sulfurospirillum. The presence of D. dehalogenans was confirmed by its partial 16S rRNA gene sequence. Conclusions Results of chemical sediment analyses demonstrated high loads of organochlorine compounds, particularly of PCDD/F. Several years after stopping the waste water discharge to Spittelwasser creek, this sediment remains a main source for pollution of the downstream river system by way of the ongoing mobilization of sediment during high floods. As indicated by our enzyme activity measurements, the decomposition potential for organic matter is low in organochlorine-rich sediment layers. In contrast, the comparably higher enzyme activities in less organochlorine-polluted sediment layers as well as the presence of physiologically active bacteria suggest a considerable potential for natural attenuation. Recommendations and Perspectives From our data we strongly recommend to explore the degradative capacity of sediment microorganisms and the limits for in situ activity towards specific sediment pollutants in more detail. This will give a sound basis for the integration of bioremediation approaches into general concepts to reduce the risk that permanently radiates from this highly contaminated sediment. Submission Editor: Dr. Henner Hollert (Henner.Hollert@urz.uniheidelberg.de)     

Evaluation of leaching and extraction procedures for soil and waste

Laboratory leaching tests may be used for source term determination as a basis for risk assessment for soil-groundwater pathways on contaminated sites. In order to evaluate different leaching procedures, batch extraction tests and percolation tests were performed using three reference materials produced from contaminated soil, demolition waste and municipal solid waste incinerator bottom ash. Emphasis was placed on the investigation of the leachability of the heavy metals copper and chromium, polycyclic aromatic hydrocarbons (PAHs) and the anions chloride and sulfate. Significant discrepancies between column experiments and batch/extraction tests were found for the release of PAHs and to a lesser extent for the heavy metals Cu and Cr. Additionally interlaboratory comparisons were conducted based on different leaching tests with the reference materials and evaluated using the criteria of comparability and reproducibility. The best reproducibility was achieved for all investigated substances in column tests. The reproducibility of batch tests was acceptable except for PAHs. The results from the experimental work will help establish standardized and feasible laboratory procedures as fundamental for substance specific risk assessment of contaminated sites.     

Method optimization to measure polybrominated diphenyl ether (PBDE) concentrations in soils of Bratislava, Slovakia

We modified an analytical method to determine polybrominated diphenyl ethers (PBDEs) in urban soils of Bratislava (Slovakia). Gel permeation chromatography (GPC) introduced as a clean-up step for soil extracts substantially reduced matrix enhancements when PBDEs were measured with gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS). The resulting method proved to be accurate, precise, and showed low detection limits. The sum of 15 PBDE concentrations in surface horizons of Bratislava soils ranged from 87 to 627 pg g⁻¹. PBDE concentrations were mostly higher in surface than deeper horizons probably because of atmospheric deposition and lack of substantial vertical transport. Lower brominated PBDEs undergo more soil-atmosphere exchanges or are more scavenged and transferred with litter fall to the soil organic matter than higher brominated ones as suggested by the correlation between lower brominated PBDEs and soil organic C (C_org) concentrations.     

Groundwater mapping: An analysis of the United States Hydrological Investigation Atlas Series

Groundwater mapping is a critical component of efficient water resource management today. Difficulties arise when highly specialized and complex groundwater data are collected and presented in map form. This is an analysis of the map content and its presentation in the USGS Hydrological Investigation Atlas Series. This analysis reveals the problems to be surmounted in mapping groundwater information. The technical nature of the groundwater data requires special design considerations.     

Decision making under uncertainty in case of soil remediation

Decisions on soil remediation are one of the most difficult management issues of municipal and state agencies. The assessment of contamination is uncertain, the costs of remediation are high, and the impacts on the environment are multiple. This paper presents a general, transparent, and consistent method for decision making among the remediation alternatives. Soil washing, phytoremediation, and no remediation are exemplarily considered. Multi-criteria utility functions including (a) the cost of remediation (b) the impact on human health and agricultural productivity, and (c) the economic gain after remediation are constructed using probability density functions representing contamination for all site coordinates. Herewith, the probability of different types of (i) correct decisions such as a hit or a true rejection and (ii) erroneous decisions such as a false alarm or miss are examined. The decision theoretic model is applied to a case study on heavy metal contaminated soil. This case study reveals the non-linear structure of multi-criteria-decision making. The case study shows that the geostatistical uncertainties of the log-normal distributed soil contamination must be taken into account: When uncertainties are not considered and the utilities are assessed according to the estimated value for a spatial unit, only few (N=26) spatial units result where the utility score of the alternative soil washing are higher than the utility score to the no remediation alternative. However, when taking into account geostatistical uncertainties of the log-normal soil distribution this number is about ten times greater (N=237). Furthermore, the use of 'maximizing expected utility' as decision rule is critical in that it may lead to a high probability of misses.     

An Evaluation of the Semi-VOST Method for Determining Emissions from Hazardous Waste Incinerators

The Semi-Volatile Organic Sampling Train method was investigated to determine its reliability and to determine the bias and precision of the method when used to determine emissions from hazardous waste incinerators. Experiments showed that the matrix and sampling variables usually involved in sampling emissions from a hazardous waste incinerator had no significant effect on the recovery of 11 different organic compounds. Significant losses of the sampled compounds can occur during sample preparation. The degree of loss appears to be directly related to the compounds, vapor pressure. These losses can be corrected for by adding deuterated surrogates to the sample and analyzing the surrogates along with the native compounds.

The bias determination was based on dynamic spiking of the sampling train with five deuterated organic compounds selected from Appendix VIII of the Resource Conservation and Recovery Act regulations. The results show biases of from -1 ± 8 percent to -18 ± 27 percent for chlorinated and nonchlorinated compounds. Pyridine, a water-soluble compound, showed a larger bias of-29 ± 13 percent. Particular attention to the recovery of water soluble compounds is necessary to minimize bias in their determinations. Further work is needed to determine the reliability of laboratory-determined retention volumes that are used to determine sampling conditions.