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The present study was elaborated within the scope of the INTAFERE (Integrated Analysis of Mobile Organic Foreign Substances in Rivers) project which investigates the occurrence of xenobiotics in small freshwater streams with particular consideration of social impact factors. The aim of this study is to investigate the seasonal and spatial variance of organic micropollutants in small fresh water streams and to identify possible sources and sinks. Therefore four small freshwater river systems in Hesse, Germany, have been investigated with respect to common organic pollutants such as: the organophosphates tri-n-butyl phosphate (TBP), tris(2-butoxyethyl)phosphate (TBEP), tris(2-chloroethyl)phosphate (TCEP), tris(1-chloro-2-propyl)phosphate (TCPP), and tris(1,3-dichloro-2-propyl)phosphate (TDCPP), the synthetic musk fragrances 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexa-methylcyclopenta-[g]-2-benzopyran (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), the endocrine disruptors bisphenol A (BPA), 4-tert-octylphenol (OP) and the technical isomer mixture of 4-nonylphenol (NP), the herbicide terbutryn [2-(t-butylamino)-4-(ethylamino)-6-(methylthio)-s-triazine] as well as the insect repellent N,N-diethyl-m-toluamide (DEET). Water samples were collected in the time span from September 2003 to September 2006 at 26 sampling locations. The samples were extracted with solid phase extraction (SPE) and analyzed by coupled gas chromatography-mass spectrometry (GC-MS). For quantification the internal standard method was used. The results of the study showed an ubiquitous occurrence of organic pollutants in the fresh water streams of the study area. The organophosphates have been detected in 90 % of the water samples with mean concentrations of 502 ng/l (TCPP), 276 ng/l (TBP), 183 ng/l (TBEP), 118 ng/l (TCEP) and 117 ng/l (TDCPP). Sewage treatment plant (STP) effluents were identified as the dominating source for the chlorinated organophosphates as well as for the synthetic musk fragrances and the insect repellent DEET in the river systems. Consequently the highest concentrations were observed in the Schwarzbach system characterized by the highest proportion of waste water compared to the other river systems. Mean concentration levels of the synthetic musk fragrances HHCB and ATHN were 141 ng/l and 46 ng/l, respectively and 124 ng/l in case of DEET. The synthetic musk fragrances showed a clear seasonal trend with significantly lower concentrations in summer times compared to winter times, which is ascribed to stronger photodegradation and volatization during summer times. In contrast, mean DEET concentrations and loads were significantly higher in summer than in autumn, winter and spring, in parallel with the main insect season. The concentrations of the endocrine disruptors BPA, NP and OP in the river water samples ranged from <20 ng/l to 1927 ng/l, <10 ng/l to 770 ng/l, and <10 ng/l to 420 ng/l, respectively. Whereas OP was present in about 2/3 of the samples, NP and BPA could only be detected in 56% and 13% of the water samples, respectively. BPA levels exceeded in two samples the predicted no-effect concentration (PNEC) for water organisms. In case of NP, highest concentrations and loads were found in September 2003 and decreased significantly since then. In contrast, concentrations and loads of OP which serves in a similar application field remained nearly constant during the sampling period. The decrease of NP can be attributed to the implementation of the European Directive 2003/53/EG, which restricts the use of nonylphenols and nonylphenol ethoxylates since January 2005. However, at the end of the sampling period in September 2006, NP could still be detected at mean concentrations of 18 ng/l in the river waters of the sampling area. Furthermore, absence of NP in several samples from associated STP effluents indicate that the STPs cannot be the only sources for NP found in the river water. The herbicide terbutryn was present in the rivers during the whole sampling period from September 2003 to September 2006 despite a ban on its use as a herbicide from January 2004 on. Terbutryn levels ranged from < 4 ng/l to 5600 ng/l, showing a clear spatial pattern with high terbutryn concentrations in the Weschnitz and Modau river systems and significantly lower terbutryn levels in Schwarzbach and Winkelbach. Results from the analysis of two STP effluents discharging into the Weschnitz and the Modau, respectively, indicate that terbutryn enters the rivers from this source. Furthermore, terbutryn concentrations and loads showed a clear seasonal trend with significantly higher levels in summer and autumn. Obviously, the ban on agricultural use of terbutryn at the end of 2003 had no discernable influence on terbutryn concentration in the rivers because there was no trend of decreasing.
Cenozoic lignite deposits are widespread across Europe, Asia, America, Australia, and Indonesia. These deposits were the subject of numerous studies on changes in regional/global paleoclimates, paleobotany, paleoenvironment, and basin evolutions, which led to the formation of these lignites. In some of these Cenozoic lignite deposit basins, a succession of pale and dark lignite layers has been described in the Miocene Lower Rhine Basin in Germany, the Oligo-Miocene Gippsland Basin in southeastern Australia, and several Mio-Pliocene basins in southwestern China. Furthermore, pale and dark lithotypes in lignite seams also have been found in some Pliocene lignite deposit basins from Slovenia, Serbia, and Poland. The widespread cyclic occurrence of pale and dark layers in lignite basins might represent alternating depositional conditions related to the changes in plant communities, the regional/global climate, the tectonic setting, the Asian monsoon, and orbital periodicity during peat formation. ...
The Late Cretaceous is known to be mostly affected by warm periods interrupted temporarily by a number of cooling events. The reconstruction of the paleoclimatic conditions during a period of high concentration of CO2 in the atmosphere is of great importance for the creation of future climate models. We applied the recently developed method reconstructing the SST from the TEX86 (TetraEther indeX of tetraethers consisting of 86 carbon atoms).
The sample material used for the present study was obtained from the tropical Late Cretaceous southern Tethys upwelling system (Negev/Israel), lasting from the Late Santonian to the Early Maastrichtian (~ 85 to 68 Ma). On the core samples from the Shefela basin, representing the outer belt of the upwelling system and the outcrop profile from the open mine Mishor Rotem (Efe Syncline), representing the inner belt, various bulk geochemical and biomarker studies were performed in this thesis.
Derived from TEX86 data, a significant long-term SST cooling trend from 36.0 to 29.3 °C is recognized during the Late Santonian and the Early Campanian in the southern Tethys margin. This is consistent with the opening and deepening of the Equatorial Atlantic Gateway (EAG) and the intrusion of cooler deep water from the southern Atlantic Ocean influencing the global SSTs and also the Tethys Ocean. Furthermore, the cooler near shore SST usually found in modern upwelling systems could be verified in case of the ancient upwelling system investigated in the present study. The calculated mean SST in the inner belt (27.7 °C) represented in the Efe Syncline was 1.5 °C cooler in comparison to the more seaward located outer belt (Shefela basin).
Moreover, geochemical and biomarker analyses were used to identify both the accumulation of high amounts of phosphate in the PM and good preservation of organic matter (OM) in the lower part of the OSM section. Total organic carbon (TOC) contents are highly variable over the whole profile reaching from 0.6 % in the MM, to 24.5 % in the OSM. Total iron (TFe) varies from 0.1 % in the PM to 3.3 % in the OSM and total sulfur (TS) varies between 0.1 % in the MM and 3.4 % in the OSM. Different correlations of TS, TOC and TFe were used to identify the conditions during the deposition of the different facies types. Natural sulfurization was found to play a key role in the preservation of the OM particularly in the lower part of the OSM. Samples from the OSM and the PM were deposited under dysoxic to anoxic conditions and iron limitation lasted during the deposition of the OSM and the PM, which effected the incorporation of sulfur into OM.
Phosphorus is highly accumulated in the sediments of the PM with a mean proportion of 11.5 % total phosphorus (TP), which is drastically reduced to a mean value of 0.9 % in the OSM and the MM. From the correlation of the bulk geochemical parameters TOC/TOCOR ratio and TP a major contribution of sulfate reducing bacteria to the phosphate deposition is concluded. This interrelation has previously been investigated in recent coastal upwelling systems off Peru, Chile, California and Namibia. This was further supported by the analysis of branched and monounsaturated fatty acids indicating the occurrence of sulfate reducing and sulfide oxidizing bacteria during the deposition.
According to the results from the analysis of n-alkanes and C27- to C29-steranes up to 95 % of the OM was of marine origin.
Organic sulfur compounds (OSC) were a major compound class in the aromatic hydrocarbon fraction and n-Alkyl and isoprenoid thiophenes were the most abundant, with highest amounts found for 2-methyl-5-tridecyl-thiophene (28 µg/g TOC). The relatively high abundance of ββ-C35 hopanoid thiophenes and epithiosteranes is equivalent to an incorporation of sulfur during the early stages of diagenesis.
Moreover, the geochemical parameters δ13Corg, δ15Norg, C/N and the pristane/phytane (Pr/Ph) ratio, were studied for reconstruction of seafloor and water column depositional environments. The high C/N ratio along with relatively low values of δ15Norg (4 ‰ to 6 ‰) and δ13Corg (-29 ‰ to -28 ‰) are consistent with a significant preferential loss of nitrogen-rich organic compounds during diagenesis. Oxygen-depleted conditions lasted during the deposition of the PM and the bottom of the OSM, reflected by the low Pr/Ph ratio of 0.11–0.7. In the upper part of the OSM and the MM the conditions changed from anoxic to dysoxic or oxic conditions. This environmental trend is consistent with co-occurring foraminiferal assemblages in the studied succession and implies that the benthic species in the Negev sequence were adapted to persistent minimum oxygen conditions by performing complete denitrification as recently found in many modern benthic foraminifera.
Furthermore, the anammox process could have influenced the nitrogen composition of the sediments. In this anaerobically process nitrite and ammonia are converted to molecular nitrogen.
Forty two samples of the Late Eocene Kiliran oil shale, Central Sumatra Basin, Indonesia were collected from a 102 m long drill core. Palynofacies and geochemical analyses have been carried out to reconstruct the paleoenvironmental conditions and paleoecology during deposition of the oil shale. Amorphous organic matter (AOM) is very abundant (>76%). B. braunii palynomorph is present (3-16%) as the only autochtonous structured organic matter and generally more abundant in middle part of the profile. The stable carbon isotopic composition of organic matter (δ13C) varies from -27.0 to -30.5‰ and is generally more depleted in middle part of the profile. The ratio of total organic carbon to sulfur (TOC/S), used as salinity indicator, ranges from 2.5 to 15.8 and shows variations along the profile. Relatively less saline environments are observed in the middle part profile. Fungal remains are generally present only in middle part of the profile with distinct peak of abundances. The presence of fungal remains is regarded as an indication for a relatively warmer climate during deposition of middle part of the profile. The warmer climate is thought to influence the establishment of a thermocline, limiting the supply of recycled nutrients to the epilimnion. Consequently, the primary productivity in the Kiliran lake decreased during deposition of the middle part of the profile as indicated by the relatively depleted δ13C and the blooming of B. braunii. The chemocline was also shoaling during deposition of the middle part of the profile according to the higher abundance of isorenieratene derivatives of green sulfur bacteria origin. The warmer climate affected also to increase of water supply and thus less saline environments.
Tectonic subsidence is also thought to be a significant factor for the development of the Kiliran lake. The Zr/Rb ratio, an indicator for grain size, ranges from 0.4 to 1.3 and generally increases upwards along the profile. Three sudden decreases of the ratio are observed, indicating rapid change to finer grain size. These decreases are interpreted to indicate rapid deepening events of the lake due to mainly periodic subsidence. During deposition of lower part of the profile, the subsidence rates might have been relatively higher than sediment and water supply rates, resulting in a higher autochtonous fraction in the oil shale. During deposition of middle part of the profile, the sediment and water supply rates were relatively higher promoting distinct progradational sedimentation. Subsequently, the lake became more shallow and smaller during deposition of the upper part of the profile, leading to a relatively higher terrigenous input to the oil shale.
Norneohop-13(18)-ene and neohop-13(18)-ene derived from methanotrophic bacteria are the dominant hopanoid hydrocarbons. The sum of their concentrations varies from 40.6 to 360.0 μg/g TOC. The δ13C of these compounds are extremely depleted (-45.2 to -50.2‰). The occurrence of abundant bacteria including methanotrophic bacteria was responsible for the recycling of carbon below the chemocline of the lake. The effect of the recycling of carbon is observed by the presence of a concomitant depletion (about 7-9‰) in 13C of some specific biomarkers derived from organisms dwelling in the whole phototrophic zone.
4-Methylsterane and 4-methyldiasterene homologues occur in the oil shale as the predominant biomarkers. The sum of the concentrations of all homologues are about 40.3-1,009.2 μg/g TOC with generally higher values in uppermost and lower parts of the profile. Ca accounts as the predominant element in the oil shale, ranging from 5.0 to 16.7%. This element shows generally parallel variation with the 4-methylsterane homologues along the profile. This suggests that the 4-methylsteranes were derived from biological sources favoring more alkaline and more trophic environments. On the other hand, these compounds were less abundant in middle part of the profile which is consistent with less alkaline and less trophic environments promoting B. braunii to bloom.
The 4-methylsterane homologues are considered to originate from Dinoflagellates. Alternation between Dinoflagellates and B. braunii in Paleogene lake systems due to water chemistry changes are known from previous studies. Moreover, freshwater Dinoflagellates have been frequently reported to occur in the basin depocenters. In the present case, distinct alternation between B. braunii abundances and concentrations of 4-methylsterane homologues along the studied oil shale profile suggest that the 4-methylsterane homologues were derived from freshwater Dinoflagellates although dinosterane is not present in the sediment extracts. Water alkalinity and trophic level changes were most likely responsible for the alternation of Dinoflagellates and B. braunii blooming.
Forty two samples of the Late Eocene Kiliran oil shale, Central Sumatra Basin, Indonesia were collected from a 102 m long drill core. The oil shale core represents the deposition time of about 240.000 years. Palynofacies and geochemical analyses have been carried out to reconstruct the paleoenvironmental conditions and paleoecology during deposition of the oil shale. Amorphous organic matter (AOM) is very abundant (>76%). B. braunii palynomorphs are present (3-16%) as the only autochtonous structured organic matter and generally more abundant in the middle part of the profile. The stable carbon isotopic composition of bulk organic matter (13C) varies from -27.0 to -30.5‰ and is generally more depleted in the middle part of the profile. The ratio of total organic carbon to sulfur (TOC/S), used as salinity indicator, ranges from 2.5 to 15.8 and shows variations along the profile. Slightly less saline environments are observed in the middle part of the profile. Fungal remains are generally present only in this part with a distinct peak of abundance. The presence of fungal remains is regarded as an indication for a relatively warmer climate during deposition of the middle part of the profile. The warmer climate is thought to influence the establishment of a thermocline, limiting the supply of recycled nutrients to epilimnion. Consequently, the primary productivity in the Kiliran lake decreased during deposition of the middle part of the profile as indicated by the relatively depleted 13C values and the blooming of B. braunii. The chemocline was also shoaling during the deposition according to the higher abundance of total isorenieratane and its derivatives originated from green sulfur bacteria dwelling in the photic zone euxinia. The warmer climate is also thought to influence the slightly decrease of water salinity during deposition of the middle part of the profile. The occurrence of B. braunii in Kiliran lake is also recognized from organic geochemical data. The distribution of n-alkanes is characterized by the unusual high amount of C27 n-alkane relative to the other long-chain n-alkanes. The concentrations of C27 n-alkane vary from 30.1 to 393.7 μg/g TOC and are generally in parallel with the abundances of B. braunii palynomorphs along the profile. The 13C values of this compound are about -31‰ and up to 2‰ enriched relative to those of the adjacent long-chain n-alkanes. B. braunii race A can thus be regarded as the significant biological source of the C27 n-alkane. Lower amounts of lycopane are observed in many oil shale samples (0 to 54.7 μg/g TOC). The 13C value of this compound is 17.2‰. This strong enrichment of 13C suggests that the lycopane was derived from B. braunii race L. The concentrations of lycopane develop generally in opposite with those of C27 μalkane. It is likely that both B. braunii races bloomed in alternation in the lake, probably due to changes on specific water chemistry. Norneohop-13(18)-ene and neohop-13(18)-ene derived from methanotrophic bacteria are the dominant hopanoid hydrocarbons. The sum of their concentrations varies from 40.6 to 360.0 μg/g TOC. The 13C of these compounds are extremely depleted (-45.2 to -50.2‰). The occurrence of abundant bacteria including methanotrophic bacteria was responsible for the recycling of carbon below the chemocline of the lake. The effect of the recycling of carbon is observed by the presence of a concomitant depletion (about 7-9‰) in 13C of some specific biomarkers derived from organisms dwelling in the whole phototrophic zone. 4-Methylsterane and 4-methyldiasterene homologues occur in the oil shale as the predominant biomarkers. The sum of the concentrations of all homologues are about 40.3-1,009.2 μg/g TOC with generally higher values in the uppermost and lower parts of the profile. Calcium (Ca) accounts as the predominant element in the oil shale, ranging from 5.0 to 16.7%. This element shows generally parallel variation with the 4-methylsterane and 4-methyldiasterene homologues along the profile. This suggests that these compounds were derived from biological sources favoring more alkaline and more trophic environments. On the other hand, these compounds were less abundant in the middle part of the profile which is consistent with less alkaline and less trophic environments promoting B. braunii to bloom. Alternation between Dinoflagellates and B. braunii in ancient lacustrine environments due to water chemistry changes have been known from previous studies. In the present case, distinct alternation between B. braunii abundances and concentrations of 4-methylsterane and 4-methyldiasterene homologues along the studied oil shale profile suggest a hypothesis that these compounds were derived from freshwater Dinoflagellates although dinosterane is not present in the sediment extracts. Water alkalinity and trophic level changes were most likely responsible for the alternation of Dinoflagellates and B. braunii blooming.
Within the present study the occurrence and fate of the organophosphorus flame retardants and plasticizers tris(2-chloroethyl) phosphate (TCEP), tris(2-chloro-1-methylethyl) phosphate (TCPP), tris(1,3-dichloro-2-propyl) phosphate (TDCP), tris(2-butoxyethyl) phosphate (TBEP), tri-iso-butyl phosphate (TiBP), and tri-n-butyl phosphate (TnBP) in precipitation, lake water, surface runoff and groundwater from urban and remote areas in Germany was investigated between June 2007 and October 2009. 255 samples of precipitation, 210 samples of lentic surface water and 72 samples of groundwater were analyzed for the six organophosphates (OPs) by solid phase extraction followed by gas chromatography-mass spectrometry. The research focused on aspects concerning (1) the atmospheric washout of OPs by precipitation, (2) the temporal variation of OP concentrations in precipitation and in lentic surface waters as well as (3) the pollution of groundwater by OPs. The results of the study emphasize the importance of precipitation as an all-season entry-pathway for OPs in the aquatic environment, particularly in densely populated urban environments with high traffic volume and abundant usage of flame-protected products. No seasonal trends were observed for all analytes in precipitation at the urban sampling site. TCPP dominated in all precipitation and storm water holding tank (SWHT) water samples with maximum levels exceeding 1 µg/L. An accumulation of OPs deposited in SWHTs was observed with concentrations often exceeding those observed in wet precipitation. Median concentrations of TCPP (880 ng/L), TDCP (13 ng/L), and TBEP (77 ng/L) at the urban SWHT were more than twice as high as those measured at the urban precipitation sampling site (403 ng/L, 5 ng/L, 21 ng/L) located close to the SWHT. OP levels in more remote lakes were often below or close to the limits of quantitation (LOQ). Nevertheless, TCPP was the substance with the highest median concentration in rural volcanic lakes (7–18 ng/L) indicating an atmospheric transport of the compound. At urban lakes the median OP concentrations were in the range of 23–61 ng/L (TCEP), 85–126 ng/L (TCPP), <LOQ–53 ng/L (TBEP), 8–10 ng/L (TiBP), and 17–32 ng/L (TnBP). In laboratory experiments, TBEP, TiBP, and TnBP were photochemically degraded in spiked lake water samples upon exposure to sunlight. In the SWHT a seasonal trend with decreasing concentrations in summer/autumn was evident for TiBP and TnBP but not for the chlorinated OPs. The decreasing concentrations can be explained by in-lake photodegradation. Results have also shown that the occurrence of OPs in groundwater is depending on the anthropogenic impact during groundwater recharge/natural replenishment. Infiltration of precipitation was found to be no important entry-pathway for OPs into aquifers at rural sites. Highest OP concentrations (>0.1 µg/L) were determined in groundwater polluted by percolating leachate from contaminated sites or groundwater recharged via bank filtration of OP-loaded recipients. Concentrations of TCEP, TCPP, TiBP and TnBP in groundwater decreased rapidly (89–97%) during bank filtration with increasing distance from the recipient due to adsorption processes and/or biotransformation. Although TCEP and TCPP are stable within the aquifer, they are not suitable as conservative organic tracers in groundwater.
The purpose of this study was to reconstruct the depositional environment, the genesis and the composition of Miocene coals in the Kutai Basin, East Kalimantan, Indonesia and to improve our understanding of the factors controlling the organic and inorganic composition, variation of biomarkers, and the peat forming vegetation of the coals. To achieve the aim methods belonging to three different disciplines were applied: 1. Coal petrology (chapter 3) 2. Inorganic geochemistry: sulfur, pyrite and mineral matter distributions (chapter 4) 3. Organic geochemistry of saturated, aromatic hydrocarbon fractions and stable carbon isotopic composition (chapter 5 and 6) Coal petrology Coal developes from peat deposited in mires, mainly in swamps and raised bogs. It is therefore necessary to consider how peat was formed in the past. Coal contains a variety of plant tissues in different degrees of preservation. Tissues of distinct origin are microscopically identifiable and can frequently be related to certain parts of the plant, such as cuticles, woody structures, spores, algal, resin, etc. Together with the particles of less certain origin they are termed macerals which are the petrographic components of coal. During and after deposition of plant remains in sedimentary basins, the organic matter will undergo a sequence of physical, biochemical and chemical changes, which finally results in the formation of coals of increasing rank depending mainly on the temperature influence. The process of coalification begins with practically unaltered plant material and peat, and continues with increasing rank through brown coal, bituminous coal, and finally to anthracite as well as graphite. Coal petrography provides valuable of data of maceral and mineral percentages with reflectance values, which can be used to reconstruct the depositional environment and the coalification processes. In lower rank coals, the material is represented by a group of macerals called huminite, and in bituminous and anthracite coals by a group of macerals called vitrinite. Coal petrography analyses have been carried out on samples from some Miocene coal seams from Kutai Basin. The study has shown that huminite reflectance values of coal samples from ...
The objective of the present doctoral thesis was to investigate the occurrence, distribution, and behaviour of six hydrophilic ethers: ethyl tert-butyl ether (ETBE), 1,4-dioxane, ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), and tetraethylene glycol dimethyl ether (tetraglyme) in surface-, waste-, ground- and drinking water samples. Solid phase extraction and gas chromatography/mass spectrometry were used to analyze the six hydrophilic ethers. Altogether more than 150 surface water samples, almost 100 of each groundwater and wastewater samples, and 10 raw and drinking water samples were analyzed during the research project.
Initially, the method was validated in order to simultaneously determine the analytes of interest in various aquatic environments. A solid phase extraction method that uses coconut charcoal (Resprep® activated coconut charcoal, Restek) or carbon molecular sieve material (SupelcleanTM Envi-CarbTM Plus, Supelco) for analyte absorption were found suitable for determination of ETBE, 1,4-dioxane, and glymes in surface-, drinking-, ground- and wastewater samples. Precision and accuracy of both methods was demonstrated for all analytes of interest. The recovery of target compounds from the ultrapure water spiked at 1.0 µg L−1 was between 86.8 % and 98.2 %, with relative standard deviation below 6 %. The samples spiked at 10.0 µg L−1 gave slightly higher recovery of 90.6 % to 112.2 % with a relative standard deviation below 3.4 % for each analyte. Detection and quantification limits in ultrapure water and surface waters were furthermore established. The limit of quantitation (LOQ) in ultrapure water ranged between 0.024 µg L−1 to 0.057 µg L−1 using Restek cartridges, and 0.030 µg L−1 to 0.069 µg L−1 using Supelco cartridges. In the surface water samples the calculated LOQ was 0.032 µg L−1 to 0.067µg L−1 using coconut charcoal material and 0.032 µg L−1 to 0.052 µg L−1 using the carbon molecular sieve material. Moreover, stability of the unpreserved and preserved water samples as well as the extracts was determined. Preservation of samples with sodium bisulfate (at 1 gram per Liter) resulted in much better stability of the ethers in water samples. Subsequently, 27 samples obtained from seven surface water bodies in Germany (Rivers Rhine, Lippe, Main, Oder, Rur, Schwarzbach and Wesel-Datteln Canal) were analyzed for the six hydrophilic ethers. ETBE was present in only two surface waters (Rhine River and Wesel-Datteln Canal) with concentrations close to the LOQ (up to 0.065 µg L−1). 1,4-Dioxane was detected in all of the water samples at concentrations reaching 1.93 µg L–1. Monoglyme was identified only in the Main and Rhine Rivers at the maximum concentration of 0.114 µg L–1 and 0.427 µg L–1, respectively. Very high concentrations (up to 1.73 µg L−1) of diglyme, triglyme, and tetraglyme were detected in the samples from the Oder River. These glymes were also detected in the Rhine River; however the concentrations did not exceed 0.200 µg L–1. Furthermore, tetraglyme was detected in the Main River at an average concentration of 0.409 µg L–1 (n = 6) and in one sample from the Rur River at 0.192 µg L–1.
Four sampling campaigns were conducted at the Oderbruch polder between October 2009 and May 2012, in order to study the behavior of the hydrophilic ethers and organophosphates during riverbank filtration and in the anoxic aquifer. Moreover the suitability of these target compounds was assessed for their use as groundwater organic tracers. At the time of each sampling campaign, concentrations of triglyme and tetraglyme in the Oder River were between 20–185 ng L–1 (n = 4) and 273¬–1576 ng L–1 (n = 4). Monoglyme, diglyme, and 1,4-dioxane were analyzed only during the two last sampling campaigns. At that time, the concentration of diglyme in Oder River was 65¬–94 ng L-1 (n = 2) and 1,4-dioxane 1610¬–3290 ng L–1 (n = 2). In the drainage ditch, following bank filtration, concentrations of ethers ranged between 1090 ng L–1 and 1467 ng L–1 for 1,4-dioxane, 23¬ng L–1 and 41 ng L–1 for diglyme, 37 ng L–1 and 149 ng L–1 for triglyme, and 496 ng L–1 and 1403 ng L–1 for tetraglyme. In the anoxic aquifer, 1,4-dioxane showed the greatest persistence during the groundwater passage. At the distance of 1150 m from the river and an estimated groundwater age of 41.9 years, a concentration above 200 ng L−1 was detected. A positive correlation was found for the inorganic tracer chloride (Cl−) with 1,4-dioxane and tetraglyme. Similarities in the behavior of Cl− and the organic compound suggested that 1,4-dioxane and tetraglyme are controlled by the same hydraulic process and therefore can be used as additional tracers to study the dynamics of the groundwater system. These results show that high concentrations of ethers are present in the surface water and are not removed during bank filtration processes. Moreover, the hydrophilic ethers persist in the anoxic aquifer and little or no degradation is expected, supporting, their possible application as organic tracers.
A separate sampling project was conducted for 1,4-dioxane that focused primarily on its fate in the aquatic environment. This study provided missing information on the extent of water pollution with 1,4-dioxane is Germany. Numerous waste-, surface-, ground- and drinking water samples were collected in order to determine the persistence of 1,4-dioxane in the aquatic environment. The occurrence of 1,4-dioxane was determined in wastewater samples from four municipal sewage treatment plants (STP). The influent and effluent samples were collected during weekly campaigns. The average influent concentrations in all four plants ranged from 262 ± 32 ng L−1 to 834 ± 480 ng L−1, whereas the average effluents concentrations were between 267 ± 35 ng L−1 and 62,260 ± 36,000 ng L−1. The source of increased 1,4-dioxane concentrations in one of the effluents was identified to originate from impurities in the methanol used in the postanoxic denitrification process. Spatial and temporal distribution of 1,4-dioxane in the river Main, Rhine, and Oder was also examined. Concentrations reaching 2,200 ng L−1 in the Oder River, and 860 ng L−1 in both Main and Rhine River were detected. The average load during the sampling was estimated to be 6.5 kg d−1 in the Main, 34.1 kg d−1 in the Oder, and 134.5 kg d−1 in the Rhine River. In all of the sampled rivers, concentrations of 1,4-dioxane increased with distance from the mouth of the river and were found to negatively correlate with the discharge of the river. In order to determine if 1,4-dioxane can reach drinking water supplies, samples from a Rhine River bank filtration site and potable water from two drinking water production facilities were analyzed for the presence of 1,4-dioxane in the raw water and finished potable water. The raw water (following bank filtration) contained 650 ng L−1 to 670 ng L−1 of 1,4-dioxane, whereas the concentration in the finished drinking water fell only to 600 ng L−1 and 490 ng L−1, respectively.
During the final project, investigations of the source identification of high glyme concentrations in the Oder River were carried out. During four sampling campaigns between January, 2012 and April, 2013, 50 samples from the Oder River in the Oderbruch region and Poland were collected. During the first two samplings in the Oderbruch polder, glymes were detected at concentration reaching 0.07 µg L-1 (diglyme), 0.54 µg L−1 (triglyme) and 1.73 µg L−1 (tetraglyme) in the Oder River. The extensive sampling campaign of the Oder River (about 500 km) in Poland helped to identify the area of possible glyme entry into the river. During that sampling the maximum concentrations of triglyme and tetraglyme were 0.46 µg L−1 and 2.21 µg L−1, respectively. A closer investigation of the identified area of pollution, helped to determine the possible sources of glymes in the Oder River. Hence, the final sampling focused on the Kaczawa River, a left tributary of the Oder River and Czarna Woda, a left tributary of Kaczawa River. Moreover, samples from an industrial wastewater treatment plant were collected. Samples from Czarna Woda stream and Kaczawa River contained even higher concentrations of diglyme, triglyme, and tetraglyme, reaching 5.18 µg L−1, 12.87 µg L−1 and 80.81 µg L−1, respectively. Finally, three water samples from a wastewater treatment plant receiving influents from a copper smelter were analyzed. Diglyme, triglyme, and tetraglyme were present at an average concentration of 569 µg L−1, 4300 µg L−1, and 65900 µg L−1, respectively in the wastewater. Further research helped to identify the source of the glymes in the wastewater. The gas desulfurization process – Solinox implemented in the nearby copper smelter uses glymes as physical absorption medium for sulfur dioxide.
Results of this doctoral research provide important information about the occurrence, distribution, and behavior of hydrophilic ethers: 1,4-dioxane, monoglyme, diglyme, triglyme, and tetraglyme in the aquatic environment. A method capable of analyzing a wide range of ether compounds: from a volatile ETBE to a high molecular weight tetraglyme was validated. 1,4-Dioxane and tetraglyme were found to be applicable as organic tracers, since they are not easily attenuated during bank filtration and the anoxic groundwater passage. The extent of water pollution with 1,4-dioxane was shown in waste-, surface-, ground-, and drinking waters. One source of extremely high concentrations of 1,4-dioxane in a municipal sewage treatment plant applying postanoxic denitrification was identified, however more information is needed on the entry of 1,4-dioxane into surface waters. Moreover, 1,4-dioxane was present in drinking water samples from river bank filtration, which demonstrates its persistence in the aquatic environment and its low degradation potential during bank filtration and subsequent water treatment. Furthermore, this was the first study that focused primarily on identifying sources of glymes in surface waters. Glymes find a widespread use in industrial sectors, hence establishing their origin in the surface water is difficult (as with 1,4-dioxane). In this work, a gas desulphurization process was identified to be a dominating source of glyme pollution in the Oder River.
Occurrence and sources of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD) in the aquatic environment
(2011)
The aim of the present study was to identify the sources of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD) into the aquatic environment and to investigate its occurrence in rivers and wastewater treatment plants (WWTPs). Therefore, TMDD was analyzed in 441 wastewater samples from influents and effluents of 27 municipal WWTPs, in 6 sludge samples, in 52 wastewater samples from 3 sewage systems of municipal WWTPs, in 489 surface samples from 24 rivers, in 9 wastewater samples of 3 paper-recycling industries and in 65 groundwater samples. TMDD was also analyzed in household paper products, in 23 samples of toilet
papers, in 5 types of paper towels and in 12 types of paper tissues. The samples were collected between 2007 and 2011. The water samples were extracted with solid phase extraction (SPE) and the household paper samples with Soxhlet extraction. Gas chromatography-mass spectrometry (GC-MS) was used for quantification purposes. Between November 2007 and January 2008, TMDD was detected in the river Rhine at Worms with permanent high concentrations (up to 1330 ng/L). The results showed that TMDD is uniformly distributed across the river at Worms. An increase of the mean TMDD concentration from approximately 500 ng/L to 1000 ng/L was registered in January 2008. Due to the minor fluctuations of the TMDD concentration during the sampling period it is expected that the input of TMDD into the river is continuous. Therefore, TMDD might rather originate from effluents of municipal WWTPs than from temporal sources. The mean TMDD load based on the analysis of 147 water samples collected in the River Rhine was 62.8 kg/d which is equivalent to 23 t/a suggesting that TMDD must be used and/or produced in high quantities in order to be found in those high concentrations. To determine if TMDD is discharged by effluents of municipal WWTPs into the rivers, 24 hours influent and effluent samples of four municipal WWTPs in the Frankfurt/Rhine-Main metropolitan region were collected during November 2008 and February 2010 and analyzed for TMDD. The TMDD influent concentrations varied between 134 ng/L and 5846 ng/L and the effluent concentrations between <LOQ (limit of quantitation) and 3539 ng/L. The TMDD elimination rates in the four WWTPs varied between 33% and 68%. The results showed that effluents of municipal WWTPs are an important source of TMDD in the aquatic environment because TMDD is not completely removed from the sewage during the wastewater treatment. Weekly and daily variations of the TMDD concentration in the influents of two municipal WWTPs indicated that both private households and indirect industrial dischargers contribute to the introduction of TMDD into the municipal sewage systems. A more detailed study of the TMDD elimination rate in the different wastewater treatment stages was carried out in the WWTP Niederrad/Griesheim in Frankfurt am Main. The results showed that the removal of TMDD is mainly carried out during the aerobic biological treatments, where the elimination rate was 46%. In contrast, during the anoxic treatment the removal efficiency was only 1.4% and during the mechanical treatment the elimination rate was 19%. To determine the sources of TMDD in the sewage, household paper products (paper tissues, toilet papers and paper towels) were analyzed for TMDD using Soxhlet extraction. TMDD was detected in 83% of the samples (n=40). The highest mean TMDD concentrations were found in recycled toilet paper (0.20 μg/g) and in paper towels (0.11 μg/g). In paper tissues and non-recycled toilet paper the mean TMDD concentrations were lower 0.080 μg/g and 0.025 μg/g respectively. According to these results the high TMDD influent concentrations found previously in municipal WWTPs (mean 1.20 μg/L) cannot be explained due to migration of TMDD from the household paper products into the sewage. Thus indirect industrial dischargers are the cause of the high influent TMDD concentrations. Effluents of municipal WWTPs with different indirect industrial dischargers (textile-, metal processing-, food processing-, electroplating-, paper-recycling- and printing ink factories) were analyzed. The highest mean TMDD concentrations were found in the effluents of municipal WWTPs that have paper-recycling (71.3 μg/L) and printing ink factories (138 μg/L) as indirect industrial dischargers. These results were confirmed by analyzing process wastewater of three paper-recycling factories located in Germany. High TMDD concentrations were detected and fluctuated between 1.83 μg/L and 113 μg/L. TMDD was also analyzed in the wastewater of a non-recycling-paper factory but its concentration was much lower (0.066 μg/L) indicating that TMDD is introduced into the processing water during the papermaking process due to the use of waste paper. Analyses of wastewater samples from different parts of the sewage pipes of a municipal WWTP in Hesse, which receives the wastewater from a printing ink factory, were carried out. The TMDD concentration in the wastewater sample from the sewage pipe of the printing ink factory was much higher (3,300 μg/L) than the TMDD concentration detected in the other wastewater samples from the sewage system (0.030 μg/L – 0.89 g/L). These results confirm the printing ink production as one of the principal sources of TMDD in the sewage. Analysis of surface water samples of the River Modau downstream from the effluent of the WWTP Nieder-Ramstadt showed TMDD concentrations of up to 28.0 μg/L. These high TMDD concentrations might be caused by the indirect wastewater discharges of a paint factory connected to the municipal sewage system. These results indicate that TMDD is introduced into the municipal WWTPs principally by indirect industrial dischargers and they are mainly paint and printing ink factories. The paper-recycling factories also represent an important source of TMDD in municipal WWTPs but indirectly. According to statements given by the representatives of two paper recycling factories neither TMDD or any other TMDD containing product is used or added during the papermaking process. Therefore, TMDD is washed out from the printing inks of the coloured waste paper and concentrated in the process wastewater in the closed water circuits of paper-recycling factories reaching rivers and municipal WWTPs. The occurrence and distribution of TMDD in surface waters in Germany was also studied. The results showed that TMDD is widely distributed across different rivers systems in the federal states of Hesse, North-Rhine-Westphalia, Bavaria, Baden-Wuerttemberg and Rhineland-Palatinate. In Hesse, TMDD was detected in the some of main rivers with mean concentrations of 812 ng/L (Schwarzbach, Hessian Ried), 374 ng/L (Kinzig), 393 ng/L (Main, at Frankfurt), 539 ng/L (Werra), 326 ng/L (Fulda), 151 ng/L (Emsbach) and 161 ng/L (Nidda). In small rivers (creeks) the mean TMDD concentrations varied between <LOQ (Diemel, Urselbach) and 1890 ng/L (Darmbach). The results showed that the TMDD concentrations in creeks are highly influenced by both effluents of WWTPs and by the distance between the sampling point and the nearest WWTP. Surface samples from sampling locations downstream from WWTPs dischargers showed higher TMDD concentrations (mean 518 ng/L) than sampling locations upstream from WWTPs dischargers (mean 35.1 ng/L). The behavior of TMDD during bank filtration was investigated at two locations, at a water utility company at the Lower River Rhine (urban area) and at the Oderbruch polder (rural area). The results indicated that TMDD is removed from the surface water by bank filtration at both sampling locations. The removal process is probably carried out in the first meters of the aquifer (hyporheic zone) by biodegradation processes, since TMDD does not tend to be absorbed by sediments and it was not found in the groundwater of monitoring wells. In groundwater samples from the Hessian Ried (n=23) TMDD was found only in five samples and the highest TMDD concentration was 135 ng/L. According to these results, TMDD does not represent a concern for drinking water in Germany, since it does not reach the groundwater with high concentrations and it has a low toxicity potential. The input of TMDD into the North Sea was estimated to be 60.7 t/a by considering the mean transported loads of TMDD by the River Rhine at Wesel (58.3 t/a) and Meuse in the Netherlands (2.40 t/a). The estimated discharge of TMDD by German municipal WWTPs (8.19 t/a) and paper-recycling factories (9.24 t/a) into rivers seems to be too low considering that the mean TMDD load in the River Rhine downstream from Wesel is 58.3 t/a. However, due to the high density of population and industries at the Lower Rhine it is expected that more relevant sources of TMDD are located along the Rhine River increasing the transported load. According to the results of this PhD project TMDD is a non-ionic surfactant contained in products, which are applied on surfaces (printing inks and paints) and has the potential to reach the aquatic environment. Therefore, TMDD should fulfill the requirement of a biodegradability of 80% established by the “Law on the Environmental Impact of Detergents and Cleaning Products” in Germany. However, due to the partial elimination rates of TMDD obtained in municipal WWTPs (between 33% and 68%) and to the absence of information about the execution of the biodegradation test on TMDD, it is unknown if TMDD is in accordance with this law. Otherwise, its use as surfactant in such products is questionable.