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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.
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.
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.