Occurrence and temporal variations of TMDD in the river Rhine, Germany

Abstract

Background, aim, and scopeThe chemical substance 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD) is a non-ionic surfactant used as an industrial defoaming agent and in various other applications. Its commercial name is Surynol 104® and the related ethoxylates are also available as Surfynol® 420, 440, 465 and 485 which are characterized by different grades of ethoxylation of TMDD at both hydroxyl functional groups. TMDD and its ethoxylates offer several advantages in waterborne industrial applications in coatings, inks, adhesives as well as in paper industries. TMDD and its ethoxylates can be expected to reach the aquatic environment due its widespread use and its physico-chemical properties. TMDD has previously been detected in several rivers of Germany with concentrations up to 2.5 µg/L. In the United States, TMDD was also detected in drinking water. However, detailed studies about its presence and distribution in the aquatic environment have not been carried out so far. The aim of the present study was the analysis of the spatial and temporal concentration variations of TMDD in the river Rhine at the Rheingütestation Worms (443.3 km). Moreover, the transported load in the Rhine was investigated during two entire days and 7 weeks between November 2007 and January 2008.Materials and methodsThe sampling was carried out at three different sampling points across the river. Sampling point MWL1 is located in the left part of the river, MWL2 in the middle part, and MWL4 in the right part. One more sampling site (MWL3) was run by the monitoring station until the end of 2006, but was put out of service due to financial constrains. The water at the left side of the river Rhine (MWL1) is influenced by sewage from a big chemical plant in Ludwigshafen and by the sewage water from this city. The water at the right side of the river Rhine (MWL4) is largely composed of the water inflow from river Neckar, discharging into Rhine 14.9 km upstream from the sampling point and of communal and industrial wastewater from the city Mannheim. The water from the middle of the river (MWL2) is largely composed of water from the upper Rhine. Water samples were collected in 1-L bottles by an automatic sampler. The water samples were concentrated by use of solid-phase extraction (SPE) using Bond Elut PPL cartridges and quantified by use of gas chromatography-mass spectrometry (GC-MS). The quantification was carried out with the internal standard method. Based on these results, concentration variations were determined for the day profiles and week profiles. The total number of analyzed samples was 219.ResultsThe results of this study provide information on the temporal concentration variability of TMDD in river Rhine in a cross section at one particular sampling point (443.3 km). TMDD was detected in all analyzed water samples at high concentrations. The mean concentrations during the 2 days were 314 ng/L in MWL1, 246 ng/L in MWL2, and 286 ng/L in MWL4. The variation of concentrations was low in the day profiles. In the week profiles, a trend of in...

A multi-family offline SPE LC-MS/MS analytical method for anionic, cationic and non-ionic surfactants quantification in surface water

“…On the other hand, TMDD was quantified in 25% of the samples with a median concentration of 347 ng/L. This compound has so far been investigated in only 2 studies [18,28], and reported at mean concentrations of about 500 ng/L, which is in accordance with our study. Finally, anionic surfactants were the most frequently quantified, and at the highest concentrations, especially LAS.…”

“…They generally focused on only one type of surfactant, anionic [6,[10][11][12][13], cationic [8,14] or non-ionic [15][16][17][18]. Very few analytical methods were developed and validated for more than one type of surfactant.…”

Identification of characteristic organic contaminants in wastewaters from modern paper production sites and subsequent tracing in a river

“…TMDD concentrations as high as 3300 g L −1 were detected in effluents of paper-recycling and printing ink producing facilities, and industrial inputs are the main source of river contamination with TMDD [18]. TMDD has been previously detected in German rivers [19,20] and has a low elimination rate during wastewater treatment that ranges from 33 to 68% [21].…”

Non-target screening analysis of river water as compound-related base for monitoring measures

“…TMDD has been recently discussed in detail as river water contaminant (Guedez et al 2009). However, the knowledge of this environmentally stable high-production volume chemical as surface water pollutant is still restricted (e.g., Hankemeier et al 1999;Kronimus et al 2006;Loraine and Pettigrove 2006).…”