Einflußfaktoren auf die Freisetzung von DOC und AOX unter ehemaligen Abwasserversickerungsflächen

Factors Influencing the Release of DOC and AOX out of Former Wastewater Infiltration Soils The influence of soil and of infiltration water quality on the release of dissolved organic carbon (DOC) and adsorbable organic halogens (AOX) from two former wastewater infiltration sites was investigated in laboratory column studies. Desorption was the most important factor influencing release processes. It depends on the amount of sorbent and sorbate and the strength of binding. Therefore, for constant irrigation rates a higher soil organic carbon content coincided with higher DOC-contents of the column effluent, while the irrigation water quality was of minor importance. Within one system the dependencies of AOX release and DOC mobilization were found to be similar. Transferring these dependencies on other systems has its limitations because of a different binding quality between sorbent and sorbate.     

GC/MS-Nontargetanalytik zur Aufklärung einer organischen Grundwasserkontamination. Teil I: Probennahme – Analytik – Identifikation der organischen Verbindungen

GC/MS Nontarget Analysis to Examine an Organic Groundwater Contamination. Part I: Sampling – Analysis – Identification GC/MS nontarget analysis is a combination of an extraction sequence and a GC/MS analysis without standards. The extraction sequence should enrich a wide range of organic substances with different chemical and physical properties. The GC/MS analysis without standards evaluates the total chromatogram whereas the possibilities of compound identification are limited. This kind of view is suited very well if the task of examinations are unknown organic contaminations and the conventional target analysis has to be expanded to a large number of compounds with the uncertainty of detecting the main contaminants. The extraction sequence is similar to the EPA 625 analysis of base/neutral and acid extractable organic compounds. Basis are liquid extraction and solid-phase extraction at different pH values. This extraction procedure covers approximately 30 % of total organic carbon of these groundwater samples from a contaminated area near a low temperature carbonization plant. Relevant groups of organic compounds analyzed in the contaminated groundwater or in the reference sample are substituted aromatics, phenols, benzoamines (anilines), and derivates of benzothiophene. Differences in the trace substance mixtures between the contaminated samples and the reference sample are demonstrated by applying modern graphical methods.     

Development of a SPME-GC Method for the Determination of Organic Compounds in Wastewater

A manual SPME method is presented for the analysis of organic compounds in industrial wastewater. 24 compounds commonly found in the wastewater of a chemical plant in northern Germany have been selected as reference compounds. Precision, linearity, and detection limits have been determined. Moreover, the effect of methanol content, pH value, salt content, and an excess of compounds on the extraction process have been studied. Several compounds have been investigated for their applicability as internal standards to quantify the compounds of interest. Since the method will later be transferred to a fully automated SPME-GC system, which will be operated directly on-site at an industrial wastewater purification plant, special attention has been paid to the analysis of real wastewater samples. In this context, the fibre stability has been studied by performing 53 extraction/desorption cycles from one wastewater sample. Neither a decrease in fibre performance nor in precision has been observed indicating that the proposed method is suitable for the analysis of real wastewater.     

Association of Humic Substances: Verification of Lambert‐Beer Law

The precision UV/Vis‐absorption spectra of a naturally occurring aquatic humic substance were measured in the range of concentration 0.003 to 1.4 g/L DOC (dissolved organic carbon). Lambert‐Beer law is well obeyed at low concentrations whereas deviations have been observed for DOC concentrations above 0.1 g/L: they are interpreted in terms of self‐solvation and formation of micelles.     

Approaches to the Immunochemical Analysis of Non-extractable Triazine Residues in Refractory Organic Substances (ROS) and Characterization of ROS

The tendency of several pesticides to form non-extractable residues requires simple and fast screening methods. Immunochemical methods can meet this demand. They are based on selective and highly sensitive antibody binding to pesticide residues exposed on refractory organic substances (ROS). s-Triazines were used as an example to show the feasibility of this approach. It was proven that under laboratory conditions atrazine was bound to ROS. Antibody recognition pointed to the availability of free ethyl and isopropyl groups exposed at the non-extractable s-triazine residue. Therefore, it is suggested on the basis of antibody selectivities that binding of atrazine to ROS may take place by substitution of the chlorine residue. In the next step, aquatic ROS isolated from surface waters located in an agricultural area were examined for non-extractable s-triazines. ROS from a lake were found to contain bound residues, whereas none were detected in the creek samples. As an outlook the feasibility of serological characterization of ROS is discussed. The novel concept of serotyping is based on the fractionation of ROS by electrophoretic techniques followed by an immunoreaction with polyclonal antibodies directed against different ROS. When immunoelectrophoresis is used, precipitation lines can be compared and checked for identity and cross-reactivity. This approach can form the basis for classifying ROS and determine similarities with unknown ROS.     

The Effects of Nutrients on Natural Organic Matter (NOM) Removal in Biological Activated Carbon (BAC) Filtration

Effective biodegradation of organic compounds is one of the major objectives while optimizing biological drinking water treatment processes. Enhancing the biological activated carbon (BAC) filter performance with nutrient addition was studied using chemically pre-treated and ozonated lake water. Three parallel pilot-scale biofilters were operated: one with phosphorus addition, one with a mixture of inorganic nutrients addition, and one as a reference. The addition of nutrients had no statistically significant influence on the natural organic matter (NOM) removal when monitored by total organic carbon (TOC), UV absorbance, and assimilable organic carbon (AOC). However, the addition of nutrients significantly increased the heterotrophic plate count (HPC) bacteria of the filter effluent, while the adenosine triphosphate (ATP) analysis of the attached bacteria did not show any increase in BAC filters. It seemed that in BAC filters the bacterial growth was limited by phosphorus, but the increased bacteria could not attach themselves during the relatively short acclimatization period.     

Changes of Acute Toxicity of Organic Chemicals to Daphnia magna in the Presence of Dissolved Humic Material (DHM)

With a series of substituted anilines, a series of substituted phenols as well as diazinon and tetrabromobisphenol-A alterations of short-term acute toxicity to the waterflea Daphnia magna have been studied in the presence of dissolved humic material (DHM). The results may be categorised as follows: No alteration in acute toxicity occurred with: tetrabromobisphenol-A, o-toluidine, 3,4-dichloroaniline, and pentachlorophenol. Toxicity decreases significantly with: diazinon, 4-chloroaniline, and 4-nitrophenol. Significant toxicity increases were observed with 2,4-dichlorophenol and 2,4,5-trichlorophenol. As demonstrated for diazinon, our study reveals that in the presence of DHM and light the chemical speciation of this chemical is altered and daughter products are produced most likely via photoactive species of DHM. Most probably the toxicity of both the parent and daughter compounds is changed as well. Alterations in acute toxicity of organic chemicals may thus be attributed to the adsorption to DHM as well as to the photoactive species mediated production of daughter products with toxicity different from that of the parent compounds.     

Spectroscopic Characterization of Fulvic Acid Fractions of a Contaminated Groundwater

Two fulvic acid (FA) samples taken from a former gas production facility in the Southwest of Germany were characterized using advanced fluorescence techniques. Steady-state fluorescence (fluorescence excitation, synchronous fluorescence) as well as time-resolved fluorescence were applied. Distinct differences between the sample B22 FA taken within the contamination plume and the sample B53 FA taken downstream were found. Comparison with a model compound for metabolites and humic substances revealed that due to the downstream passage the characteristics of the dissolved organic matter became more humic-like. The assignment of single classes of compounds in the sample B22 FA is discussed in terms of their synchronous fluorescence spectra and fluorescence decay time distribution.     

Volatile Organic Sulfur Compounds in a Meromictic Alpine Lake

The full spectrum of volatile sulfur compounds was detected in the water column of the permanently stratified meromictic Lake Cadagno. Besides hydrogen sulfide it included methanethiol, carbonyl sulfide, dimethyl sulfide, carbon disulfide, and dimethyl disulfide. Their distribution in the water column suggests that these compounds are of biogenic origin. Except for carbon disulfide which is present in all layers of Lake Cadagno, these volatile organic sulfur compounds are restricted to the anoxic part of the lake. For methanethiol, dimethyl sulfide, and carbon disulfide maximum concentrations were observed in the redox transition zone and in the sediment porewater. Carbon disulfide is the most abundant volatile organic sulfur compound with concentrations of up to 60 μmol L^–1. The concentrations of the methylated sulfides are in the nmolar range. Although their concentrations varied during the summer months, seasonal trends of the concentrations of volatile organic sulfur compounds did not follow a consistent pattern. The restriction of most sulfur species to the anoxic layers of the lake indicates that their production originates from anaerobic microbial degradation of biomass and not from its release from a specific precursor like dimethylsulfoniumpropionate as in marine environments.     

Acid Rain and Natural Organic Matter (NOM)

Twentyfive years of research on the effects of acid rain on rivers and lakes has, to a very small extent, documented changes in the nature and properties of natural organic matter (NOM). In Western Norway, a "whole-watershed-artificial-acidification-experiment" took place in the period 1988–1996. The goals of this long-term experiment were to study the role of NOM in acidification of surface water and the effects of acid precipitation on the quality and properties of NOM. In the HUMEX project (Humic Lake Acidification Experiment) one half of a lake and the corresponding catchment was artificially acidified with H₂SO₄ and NH₄NO₃ over a period of 5 years. The other half of the lake and catchment served as a control. In addition to monitoring of the general chemical composition of the water from the two lake halves, a number of other chemical and biological characteristics were studied. Here, we report the results related to changes in the nature and chemical properties of NOM. During the first few years of acidification, a significantly lower concentration of NOM was recorded in the acidified half of the catchment, compared with the control. However, statistical analyses of all data (covering a 2-years pre-treatment period and 5 years of treatment) related to the concentration of NOM (TOC, colour, and UV absorbance) did not suggest any significant effect on the quantity of NOM. This apparent discrepancy between the initial decrease in the concentration of NOM and no effect when the whole 5-years period is considered, may be due to the results of two different simultaneous processes. The results suggest that there first was a reduction of TOC and colour, as a consequence of the acidification, followed by an increase, perhaps owing to increased fertilisation (nitrogen) and in addition to a general temperature increase during the period. In addition, short-term studies of the aquatic surface microlayers, lipophilicity of the NOM, content of organic sulfur, and molecular size indicate differences in the quality of the NOM between the two lake halves, which could affect light absorption.