Peter Herzsprung

Variations of DOM Quality in Inflows of a Drinking Water Reservoir: Linking of van Krevelen Diagrams with EEMF Spectra by Rank Correlation

Elevated concentrations of dissolved organic matter (DOM) such as humic substances in raw water pose significant challenges during the processing of the commercial drinking water supplies. This is a relevant issue in Saxony, Central East Germany, and many other regions worldwide, where drinking water is produced from raw waters with noticeable presence of chromophoric DOM (CDOM), which is assumed to originate from forested watersheds in spring regions of the catchment area. For improved comprehension of DOM molecular composition, the seasonal and spatial variations of humic-like fluorescence and elemental formulas in the catchment area of the Muldenberg reservoir were recorded by excitation emission matrix fluorescence (EEMF) and ultrahigh-resolution mass spectrometry (FT-ICR-MS). The Spearman rank correlation was applied to link the EEMF intensities with exact molecular formulas and their corresponding relative mass peak abundances. Thereby, humic-like fluorescence could be allocated to the pool of oxygen-rich and relatively unsaturated components with stoichiometries similar to those of tannic acids, which are suspected to have a comparatively high disinfection byproduct formation potential associated with the chlorination of raw water. Analogous relationships were established for UV absorption at 254 nm (UV(254)) and dissolved organic carbon (DOC) and compared to the EEMF correlation.

Microbial Fe(III) Reduction in Acidic Mining Lake Sediments after Addition of an Organic Substrate and Lime

To elucidate the role of Fe(III) reduction in mining lake sediments amended with organic substrates, we performed a large (10 m diameter) enclosure experiment in which sediments were amended with Carbokalk, a waste product from sugar industry containing organic carbon and lime. Fe(III) reduction rates were determined monthly by measuring the accumulation of Fe(II) in the sediments in the field. Fe(III) reduction rates were also determined by incubating sediment samples with synthetic Fe(III) oxyhydroxide under in situ temperature in the laboratory. Sulfate reduction was selectively inhibited in the Fe(III) reduction experiments by addition of sodium molybdate. Sulfate reduction was measured by accumulation of reduced inorganic sulfides in the field and by 35S radiotracer using a core injection technique. Sediment incubation and determination of sulfate reduction rates with radiotracer showed that sulfate reduction and direct microbial Fe(III) reduction occured simultaneously in the upper centimeters of the sediments and that both processes contributed to alkalinity generation. However, Fe(III) reduction was the initial process and rates were at least 3.5 fold higher than sulfate reduction rates. The results indicate that the presence of suitable anions for Fe(II) precipitation as carbonate or sulfide is needed in order to prevent loss of potential alkalinity by Fe(II) diffusion and reoxidation in the water column.

Reservoirs as sentinels of catchments: the Rappbode Reservoir Observatory (Harz Mountains, Germany)

Reservoirs can be viewed as sentinels of their catchments and a detailed monitoring of reservoir systems informs about biogeochemical and hydrological processes at the catchment scale. We developed a comprehensive online monitoring system at Rappbode reservoir, the largest drinking water reservoir in Germany, and its inflows. The Rappbode Reservoir Observatory comprises of a set of online-sensors for the measurement of physical, chemical, and biological variables and is complemented by a biweekly limnological sampling schedule. Measurement stations are deployed at the four major inflows into the system, at the outlets of all pre-reservoirs, as well as in the main reservoir. The newly installed monitoring system serves both scientific monitoring and process studies, as well as reservoir management. Particular emphasis is paid to the monitoring of short-term dynamics and many variables are measured at high temporal resolution. As an example, we quantitatively documented a flood event which mobilised high loads of dissolved organic carbon and changed the characteristics of the receiving reservoir from eutrophic to dystrophic within a few days. This event could have been completely missed by conventional biweekly sampling programs, but is relevant for biogeochemical fluxes at the catchment scale. We also show that the high frequency data provide a deeper insight into ecosystem dynamics and lake metabolism. The Rappbode Reservoir Observatory; moreover, offers a unique study site to apply, validate, and develop state of the art lake models to improve their predictive capabilities.

Functions of Straw for In Situ Remediation of Acidic Mining Lakes

The addition of straw in combination with ‘Carbokalk’, a by-product from the sugar-industry, was successfully used to stimulate microbial alkalinity generation in an acidic mining lake. To get detailed information about functions of straw, anenclosure experiment was carried out. Straw bundles were placedat the sediment surface of an acidic mining lake (ML 111) and thephysiochemical conditions and the microbiology of the sediment-water contact zone were studied. Straw was degraded by anaerobic microorganisms and dissolved organic carbon (DOC) leached from straw bundles. Pigmented flagellates responded to the DOC supply in the water column anda considerable amount of algal carbon was transported to the sediment. Straw addition led to microbial reduction of iron andsulfate in the sediment. Sulfate reduction was observed at a pHof 5.5. The pH, however, was not high enough to precipitate H2S completely. Thus, some H2S diffused into the watercolumn, where it was reoxidized. Straw did not create orstabilize an anoxic water body above the sediment. Microbial sulfate reduction and pyrite formation only took place in the sediment,whereas iron reduction also took place in the straw. Straw, however, altered the flow conditions above the sediment surfaceand prevented complete mixing of the profundal water. Straw didnot serve as a substratum for a reactive biofilm. We conclude that the most important function of straw for mining lake remediation is to be a long-term nutrient source for microbialalkalinity generation in the sediment.

Understanding molecular formula assignment of Fourier transform ion cyclotron resonance mass spectrometry data of natural organic matter from a chemical point of view.

AbstractFormula assignment is one of the key challenges in evaluation of dissolved organic matter analyses using ultrahigh resolution mass spectrometry (FTICR MS). The number of possible solutions for elemental formulas grows exponentially with increasing nominal mass, especially when non-oxygen heteroatoms like N, S or P are considered. Until now, no definitive solution for finding the correct elemental formula has been given. For that reason an approach from the viewpoint of chemical feasibility was elucidated. To illustrate the new chemical formula assignment principle, a literature data set was used and evaluated by simplified chemical constraints. Only formulas containing a maximum of one sulphur and five nitrogen atoms were selected for further data processing. The resulting data table was then divided into mass peaks with unique component solutions (singlets, representing unequivocal formula assignments) and those with two or more solutions (multiple formula assignments, representing equivocal formula assignments). Based on a [double bond equivalent (DBE) versus the number of oxygen atoms (o)] frequency contour plot and a frequency versus [DBE minus o] diagram, a new assessment and decision strategy was developed to differentiate multiple formula assignments into chemically reliable and less reliable molecular formulas. Using this approach a considerable number of reliable components were identified within the equivocal part of the data set. As a control, a considerable proportion of the assigned formulas deemed to be reliable correspond to those which would have been obtained by CH2-based Kendrick mass defect analysis. We conclude that formula assignment in complex mixtures can be improved by group-wise decisions based on the frequency and the [DBE minus o] values of multiple formula assignments. Graphical AbstractA typical frequency versus [DBE − o] diagram and assessment of molecular classes for their reliability

Quality of dissolved organic matter affects planktonic but not biofilm bacterial production in streams.

Streams and rivers are important sites of organic carbon mineralization which is dependent on the land use within river catchments. Here we tested whether planktonic and epilithic biofilm bacteria differ in their response to the quality of dissolved organic carbon (DOC). Thus, planktonic and biofilm bacterial production was compared with patterns of DOC along a land-use gradient in the Bode catchment area (Germany). The freshness index of DOC was positively related to the proportion of agricultural area in the catchment. The humification index correlated with the proportion of forest area. Abundance and production of planktonic bacteria were lower in headwaters than at downstream sites. Planktonic production was weakly correlated to the total concentration of DOC but more strongly to quality-measures as revealed by spectra indexes, i.e. positively to the freshness index and negatively to the humification index. In contrast to planktonic bacteria, abundance and production of biofilm bacteria were independent of DOC quality. This finding may be explained by the association of biofilm bacteria with benthic algae and an extracellular matrix which represent additional substrate sources. The data show that planktonic bacteria seem to be regulated at a landscape scale controlled by land use, whereas biofilm bacteria are regulated at a biofilm matrix scale controlled by autochthonous production. Thus, the effects of catchment-scale land use changes on ecosystem processes are likely lower in small streams dominated by biofilm bacteria than in larger streams dominated by planktonic bacteria.

Effects of benthic filamentous algae on the sediment-water interface in an acidic mining lake

Natural alkalinity generation by microbial sulphate reduction in acidic lakes is usually inhibited by the low pH and a low primary production which results in a lack of suitable organic carbon sources. In some acidic mining lakes mass developments of filamentous benthic algae occur. The effects of this periphyton layer on the biogeochemistry of the sediment–water interface were investigated by in situ microsensor measurements and laboratory incubations in Mining Lake Grünewalder Lauch (Germany). Microsensor measurements showed that the oxic–anoxic boundary was located in the periphyton layer and was moving up and down depending on light triggered photosynthesis. The sediment itself was permanently anoxic. The diurnal redox shift and the maintenance of neutral conditions in the periphyton layer lead to an effective precipitation of iron and phosphorus. Under the periphyton layer very high sulphate reduction rates up to 265 nmol cm−3 d−1 were measured in the sediment. These are the highest rates reported for mining lakes so far. The microbial activity was high enough to keep the pH in the surface sediment neutral and contributed to natural alkalinity production.

Chemical Changes in Sediment Pore-Waters of an Acidic Mining Lake After Addition of Organic Substrate and Lime for Stimulating Lake Remediation

In the past five years, enclosures have beeninstalled in an acidic mining lake in Lusatia to investigate insitu remediation processes. They were treated with straw, withstraw and Carbokalk, or with Carbokalk alone, where Carbokalkis a by-product of the sugar industry (solid precipitate ofnon-sugars after lime clarification of extracted sugar beetjuice). Sediment samples were taken as cores to get informationabout the behaviour of organic and inorganic components insediment pore-water with depth. Vertical distributions of pH,soluble reactive phosphate, nitrate, ammonium, silica,aluminium, iron, manganese, calcium, magnesium, sodium,potassium, sulphate, and DOC were measured. The resultingprofiles, each consisting of 15 data points at differentdepths, were compared by cluster analysis. The similarities ofsediment cores from different treated enclosures relating toprofiles of chemical components were discussed. Increasedconcentrations of potassium and sulphate were found in pore-water after substrate treatment. The data imply dissolution ofpotassium iron sulphate hydroxide minerals (jarosite) after anincrease of pH caused by dissolution of lime and by sulphatereducing processes which were stimulated by organic substrateaddition.

Limnology of sulfur-acidic lignite mining lakes. I. Physical properties: Influence of dissolved substances on electrical conductivity and density

Over one hundred post-mmmg pit lakes already exist in the former GDR and more will come. These lakes vary in their content of dissolved substances depending on rhe lake type, the origin of the water, the pits location in the groundwater field and rhe narure of the geological substrarum (ScHULTZE & GELLER 1996). Exrreme acidification or salinization was found in the mining lakes of Germany (I<LAPPER & SCHULTZE 1995, SCHIMMELE 1995a). In panicular, the strongly acidified lakes (pH <3) show high concenrrations of sulfate and iron (FRIESE et al. 1998), and are brown to red in color. The geogenic acidification is caused by microbial oxidation of pyrite and markasite in the aerated overburden (eoLMER & HINKLE 1947, PRONK &}OHNSON 1992). The resulting acidiry is then transponed by groundwater into the lake. Typical electrical conductivities (K25) of such lakes are in the range of 1-5 mS/cm (SCHIMMELE 1998). In some cases, an additional impact on the water quality arises from the dumping of industria! and municipal waste and sewage near the lakes or even directly into rhem. The chemical composition influences rhe measurement of some properties, e.g. electrical conductivity (SCHIMMELE 1998), in these waters. Furthermore, it directly affects rhe density structure and the light levels, and therefore, the stratification, rhe biological development, and rhe formation of oxic/ anoxic layers in the water (SCHIMMELE 1995b).

Photochemical degradation of natural organic sulfur compounds (CHOS) from iron-rich mine pit lake pore waters--an initial understanding from evaluation of single-elemental formulae using ultra-high-resolution mass spectrometry.

In order to better understand the chemical diversity of dissolved organic matter (DOM) in iron-rich mine waters, a variety of sediment pore waters was analysed by means of ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS). A considerable number of the DOM elemental formulae were found to contain sulfur. In a rather simplified experiment, DOM was exposed to sunlight in the presence of dissolved ferric iron, which is common in the oxygenated acidified epilimnetic waters of mine pit lakes. The photochemical alteration of the CHOS (carbon-, hydrogen-, oxygen- and sulfur-containing) compounds was then categorised by following the changes in signal intensity of mass peaks. Nearly 20,000 elemental compositions were identified and sorted into the following categories: totally degraded, partially degraded, not significantly degraded, minor new photoproducts, and newly formed photoproducts. A large proportion of the CHOS compounds were found to be entirely degraded; the degradation ratios exceeded those of the CHO compounds. The pools of totally degraded compounds and those of newly formed products were contrasted with respect to photochemically relevant mass differences. These results indicate that photochemical loss of sulfur-containing low molecular weight compounds can be considered likely. One feasible explanation is the photodegradation of sulfonic acids within the CHOS pool eventually leading to the release of sulfate.