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)     

A Variance Estimator for Constrained Estimates of Change in Relative Categorical Frequencies

Consistent estimators of change and state becomes an issue when sample data come from a mix of permanent and temporary observation units. A joint maximum likelihood estimator of state and change creates estimates of state that depend on antecedent viz. posterior survey results and may differ from estimates of state derived from a single-date analysis of the sample data. A constrained estimator of change in relative categorical frequencies that eliminates this potential inconsistency is proposed and a model based estimator of their sampling variance is developed. The performance of the constrained estimator is quantified against six criteria and a joint maximum likelihood estimator in simulated sampling from 15 populations with three combinations of permanent and temporary samples, four to six categorical class attributes, and constant size between sampling dates. Bias of the constrained estimators was negligible but larger than for joint maximum likelihood estimators. Mean absolute deviations and variances of constrained estimators were generally at par with the joint estimators. Constrained estimators of root mean square errors and achieved coverage of nominal confidence intervals of constrained estimators were occasionally better. A generalized variance function for the constrained estimates of change is provided as a computational shortcut.     

Determining Ecoregions for Environmental and GMO Monitoring Networks

A representative environmental monitoring network at the regional scale cannot use raster-based or random sampling designs, but requires a stratified sampling procedure integrating different information layers, and it has to occur in ecologically differing homogeneous regions (ecoregions). These we have determined using a set of spatial strata with ecological variables which we analysed with classification and regression trees (CART). We present a framework for environmental monitoring, that covers different scales, and we transfer the framework to a potential GMO (genetically modified organisms) monitoring network. We use ecoregion and other environmental strata together with existing environmental monitoring networks to determine GMO monitoring sites more precisely.     

Climate impact from peat utilisation in Sweden

The climate impact from the useof peat for energy production in Sweden hasbeen evaluated in terms of contribution toatmospheric radiative forcing. This wasdone by attempting to answer the question`What will be the climate impact if onewould use 1 m<sup>2</sup> of mire for peatextraction during 20 years?'. Two differentmethods of after-treatment were studied:afforestation and restoration of wetland.The climate impact from a peatland –wetland scenario and a peatland –forestation – bioenergy scenario wascompared to the climate impact from coal,natural gas and forest residues.Sensitivity analyses were performed toevaluate which parameters that areimportant to take into consideration inorder to minimize the climate impact frompeat utilisation. In a `multiple generationscenario' we investigate the climate impactif 1 Mega Joule (MJ) of energy is produced every yearfor 300 years from peat compared to otherenergy sources.The main conclusions from the study are:?The accumulated radiative forcing from the peatland – forestation – bioenergy scenario over a long time perspective (300 years) is estimated to be 1.35 mJ/m²/m² extraction area assuming a medium-high forest growth rate and medium original methane emissions from the virgin mire. This is below the corresponding values for coal 3.13 mJ/ m²/ m² extraction area and natural gas, 1.71 mJ/ m²/ m² extraction area, but higher than the value for forest residues, 0.42 mJ/ m²/ m² extraction area. A `best-best-case' scenario, i.e. with high forest growth rate combined with high `avoided' methane (CH₄) emissions, will generate accumulated radiative forcing comparable to using forest residues for energy production. A `worst-worst-case' scenario, with low growth rate and low `avoided' CH₄ emissions, will generate radiative forcing somewhere in between natural gas and coal.?The accumulated radiative forcing from the peatland – wetland scenario over a 300-year perspective is estimated to be 0.73 –1.80 mJ/ m²/ m² extraction area depending on the assumed carbon (C) uptake rates for the wetland and assuming a medium-high methane emissions from a restored wetland. The corresponding values for coal is 1.88 mJ/ m²/ m² extraction area, for natural gas 1.06 mJ/ m²/ m² extraction area and for forest residues 0.10 mJ/ m²/ m² extraction area. A `best-best-case' scenario (i.e. with high carbon dioxide CO<sub>2</sub>-uptake combined with high `avoided' CH₄ emissions and low methane emissions from the restored wetland) will generate accumulated radiative forcing that decreases and reaches zero after 240 years. A `worst-worst-case' (i.e. with low CO<sub>2</sub>-uptake combined with low `avoided' CH₄ emissions and high methane emissions from the restored wetland) will generate radiative forcing higher than coal over the entire time period.?The accumulated radiative forcing in the `multiple generations' – scenarios over a 300-year perspective producing 1 MJ/year is estimated to be 0.089 mJ/ m<sup>2</sup> for the scenario `Peat forestation – bioenergy', 0.097 mJ/ m² for the scenario `Peat wetland with high CO<sub>2</sub>-uptake' and 0.140 mJ/ m<sup>2</sup> for the scenario `Peat wetland with low CO₂-uptake'. Corresponding values for coal is 0.160 mJ/ m², for natural gas 0.083 mJ/ m² and for forest residues 0.015 mJ/ m². Using a longer time perspective than 300 years will result in lower accumulated radiative forcing from the scenario `Peat wetland with high CO₂-uptake'. This is due to the negative instantaneous forcing that occurs after 200 years for each added generation.?It is important to consider CH₄ emissions from the virgin mire when choosing mires for utilization. Low original methane emissions give significantly higher total climate impact than high original emissions do.?Afforestation on areas previously used for peat extraction should be performed in a way that gives a high forest growth rate, both for the extraction area and the surrounding area. A high forest growth rate gives lower climate impact than a low forest growth rate.?There are great uncertainties related to the data used for emissions and uptake of greenhouse gases in restored wetlands. The mechanisms affecting these emissions and uptake should be studied further.     

Chemical Composition and Acidity of Rain at the Gulf of Iskenderun,North-East Mediterranean

The purpose of the present work was to investigate the chemistry of rain in the Gulf of Iskenderun, North East Mediterranean, Turkey. The Gulf region has a large number of industries. Main industries existing in the region are iron and steel works, fertilizer plants, a cement plant, and several medium and mini size steel mills in addition to the international pipe line terminals. This study aims to apportion the local sources contributing to the overall pollution of the region. To this end a precipitation sampling program was started in January 2000, and over 48 precipitation samples were collected from each of 5 stations located at Iskenderun city center, Iskenderun industrial zone, Payas city center, the campus of Iskenderun Technical College and the campus of Mustafa Kemal University. Samples were analysed for pH, NO₃ ⁺, Cl^-. Ca, Al, Ba, Na, Cd, Co, Cr, Cu, Pb, Li, Mg, Mn, Ni, Zn, Fe, K. Concentrations of metal ions were determined by ICP-AES. NO₃ ^- ions and pH were determined by using NO₃ ^- selective electrode and pH meter, respectively.pH values of the collected samples at the industrial zone and at Payas city center, ranged between 5.02 and 7.38, respectively. NO₃ ^- and metal ions concentrations were highly variable. Concentrations of Ca and Fe ions were higher in the industrial zone and Payas city center. In the other three stations, concentrations of metal ions and NO₃ ^- ion were lower than that of industrial zone and the values of pH ranged between 6 and 7.4. The average pH values at Iskenderun Gulf showed that the precipitation was not acidic, because of the high concentration of Ca. The highest concentrations of Na and Cl ions were recorded in the University campus because the campus is located by the Mediterranean Sea.