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

Background, aim, and scope

The 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 methods

The 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.

Results

The 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 increasing TMDD concentrations was detected particularly in January 2008, when TMDD concentrations reached values up to 1,330 ng/L in MWL1. The mean TMDD concentrations during the week profiles were 540 ng/L in MWL1, 484 ng/L in MWL2, and 576 ng/L in MWL4. The loads of TMDD were also determined and revealed to be comparable in all three sections of the river. The chemical plant located at the left side of the Rhine is not contributing additional TMDD to the river. The load of TMDD has been determined to be 62.8 kg/d on average during the entire period. By extrapolation of data obtained from seven week profiles the annual load was calculated to 23 t/a.

Discussion

The permanent high TMDD concentrations during the investigation period indicate an almost constant discharge of TMDD into the river. This observation argues for effluents of municipal wastewater treatment plants as the most likely source of TMDD in the river. Another possible source might be the degradation of ethoxylates of TMDD (Surfynol® series 400), in the WWTPs under formation of TMDD followed by discharge into the river. TMDD has to be considered as a high-production-volume (HPV) chemical based on the high concentrations found in this study. In the United States, TMDD is already in the list of HPV chemicals from the Environmental Protection Agency (EPA). However, the amount of TMDD production in Europe is unknown so far and also the biodegradation rates of TMDD in WWTPs have not been investigated.

Conclusions

TMDD was found in high concentrations during the entire sampling period in the Rhine river at the three sampling points. During the sampling period, TMDD concentrations remained constant in each part of the river. These results show that TMDD is uniformly distributed in the water collected at three sampling points located across the river. ‘Waves’ of exceptionally high concentrations of TMDD could not be detected during the sampling period. These results indicate that the effluents of WWTPs have to be considered as the most important sources of TMDD in river Rhine.

Recommendations and perspectives

Based also on the occurrence of TMDD in different surface waters of Germany with concentrations up to 2,500 ng/L and its presence in drinking water in the USA, more detailed investigations regarding its sources and distribution in the aquatic environment are required. Moreover, the knowledge with respect to its ecotoxicity and its biodegradation pathway is scarce and has to be gained in more detail. Further research is necessary to investigate the rate of elimination of TMDD in municipal and industrial wastewater treatment plants in order to clarify the degradation rate of TMDD and to determine to which extent effluents of WWTPs contribute to the input of TMDD into surface waters. Supplementary studies are needed to clarify whether the ethoxylates of TMDD (known as Surfynol 400® series) are hydrolyzed in the aquatic environment resulting in formation of TMDD similar to the well known cleavage of nonylphenol ethoxylates into nonylphenols. The stability of TMDD under anaerobic conditions in groundwater is also unknown and should be studied.

     

Characterization of On-Road Vehicle NO Emissions by a TILDAS Remote Sensor

ABSTRACT

A tunable infrared laser differential absorption spectrometer (TILDAS) was used to remotely sense the nitric oxide (NO) emissions from 1,473 on-road vehicles. The real-world measurement precision of this instrument in the limit of low NO concentration is 5 ppm of the vehicle exhaust, which corresponds to a 3o detection limit of 15 ppm. Our analysis of the distribution of negative concentration measurements produced during this experiment supports this claim, showing that the instrumental noise for this set of measurements was at most 8 ppm in the limit of low NO concentration. The high sensitivity of this instrument allowed us to measure the NO emissions of even the cleanest vehicles. The measured vehicle fleet NO emissions closely fit a gamma distribution with 10% of the fleet contributing about 50% of the total fleet emissions. Newer vehicles had lower NO emissions than older ones, but high NO emitters were found in every vehicle age cohort. On a vehicle-by-vehicle basis, NO emissions correlated very weakly with vehicle velocity, acceleration, power per unit mass, carbon monoxide (CO) emissions, and hydrocarbon (HC) emissions. High NO emitting vehicles could not be identified by remote sensing of CO or HC emissions and vice versa. When we compared the NO emissions for 117 vehicles measured more than one time, about half of the high NO emitters were found to be very consistent, while the other half varied significantly.     

Gender differences in driver's license theory test scores in the Netherlands

INTRODUCTION: Gender differences were investigated in a sample of persons (N=34,755) who completed the driver's license theory test in the Netherlands. RESULTS: Contrary to recent findings from Sweden, no gender differences were found. IMPACT OF INDUSTRY: The present study signifies the importance of standardization in driver testing.     

Glacier protection laws: Potential conflicts in managing glacial hazards and adapting to climate change

The environmental, socioeconomic and cultural significance of glaciers has motivated several countries to regulate activities on glaciers and glacierized surroundings. However, laws written to specifically protect mountain glaciers have only recently been considered within national political agendas. Glacier Protection Laws (GPLs) originate in countries where mining has damaged glaciers and have been adopted with the aim of protecting the cryosphere from harmful activities. Here, we analyze GPLs in Argentina (approved) and Chile (under discussion) to identify potential environmental conflicts arising from law restrictions and omissions. We conclude that GPLs overlook the dynamics of glaciers and could prevent or delay actions needed to mitigate glacial hazards (e.g. artificial drainage of glacial lakes) thus placing populations at risk. Furthermore, GPL restrictions could hinder strategies (e.g. use of glacial lakes as reservoirs) to mitigate adverse impacts of climate change. Arguably, more flexible GPLs are needed to protect us from the changing cryosphere.     

Fate of large-scale vortices in idealized tidal lagoons

Environmental Fluid Mechanics - The generation and evolution of tidally-induced vortices in coastal and estuarine regions can influence water quality and sedimentary processes. These effects must...     

Cycling Skill Inventory: Assessment of motor–tactical skills and safety motives

Abstract

Objective: It is well established within the traffic psychology literature that a distinction can be made between driving skill and driving style. The majority of self-report questionnaires have been developed for car drivers, whereas only limited knowledge exists on the riding skill and style of cyclists. Individual differences in cycling skills need to be understood in order to apply targeted interventions.

Methods: This study reports on a psychometric analysis of the Cycling Skill Inventory (CSI), a self-report questionnaire that asks cyclists to rate themselves from definitely weak to definitely strong on 17 items. Herein, we administered the CSI using an online crowdsourcing method, complemented with respondents who answered the questionnaire using paper and pencil (n?=?1,138 in total). Our analysis focuses on understanding the major sources of variance of the CSI and its correlates with gender, age, exposure, and self-reported accident involvement as a cyclist.

Results: The results showed that 2 components underlie the item data: Motor–tactical skills and safety motives. Correlational analyses indicated that participants with a higher safety motives score were involved in fewer self-reported cycling accidents in the past 3 years. The analysis also confirmed well-established gender differences, with male cyclists having lower safety motives but higher motor–tactical skills than female cyclists.

Conclusions: The nomological network of the CSI for cyclists is similar to that of the Driving Skill Inventory for car drivers. Safety motives are a predictor of self-reported accident involvement among cyclists.     

A simulator study of driving behavior and mental workload in mixed-use arterial road environments

Objectives: Mixed-use urban environments, such as arterial roads with adjacent commercial land uses, represent crash locations with the highest risk. These locations are often characterized by high volumes of motor vehicle traffic, on-street parking, and interactions with multiple road user groups such as pedestrians, cyclists, and public transportation. The objective of this study was to investigate previously identified crash risk factors for mixed-use urban environments and assess how parking occupancy, center medians, and cyclist volume influence performance and workload in a driving simulator study.

Methods: Thirty participants were recruited for the study. Participants completed 6 drives that presented different combinations of cyclist volume, median condition, and parking occupancy. Incorporated into the simulator drives was a secondary peripheral detection task (PDT) designed to measure mental workload. Participants provided subjective assessments of workload using the Rating Scale Mental Effort (RSME).

Results: Mean lateral lane position was found to significantly vary across the 3 independent variables of parking occupancy, cyclist volume, and median conditions. No significant changes were identified for mean speed across the conditions. Subjective and objective measures of workload identified changes due to the presence of cyclists with slower reaction times for the PDT task when cyclists were present.

Conclusion: The findings provide insight into the interaction of road design elements in mixed-use urban road environments and demonstrate that increasingly complex environments increase driver demand. This has important road design implications for mixed-use arterial roads, which are often characterized by complex interactions between multiple road user groups.     

Conservation impacts of commercial cultivation of endangered and overharvested plants

Overharvesting is one of the greatest threats to species survival. Farming overharvested species is a conservation strategy that can meet growing market demand and conserve wild populations of the target species. This strategy is compatible with the international community's desire to uphold the right of local communities to use biological resources to support their livelihoods. However, studies investigating whether farming can alleviate poaching pressure have focused almost exclusively on animals. To address the shortfall in plant-focused studies, we compiled information on commercial cultivation of threatened plants to assess its conservation benefits. Because China's rising middle class has rapidly intensified demand for wildlife products, we searched the scientific literature published in Chinese (China National Knowledge Infrastructure and Baidu) and in English. We found 32 reports that contained data on 193 internationally or nationally threatened plant species that were under commercial cultivation. These reports showed that cultivations of 82% of the 193 species were sustained by collecting whole plants from the wild periodically or continuously. Although based on a small sample size, species that were maintained in cultivation only through artificial propagation or seeds collected in the wild were likely associated with a reported reduction in wild harvesting of whole plants. Even so, results of correlation analyses suggested that production system, scale, and when a species began being cultivated had little effect on conservation status of the species, either globally or in China. However, species brought into cultivation relatively recently and on a smaller scale were more likely to have undergone a reduction in collecting pressure. Farming of nonmedicinal plants was most problematic for species conservation because wild plants were laundered (i.e., sold as cultivated plants). For effective conservation, policy to guide cultivation operations based on the target species’ biological characteristics, cultural significance, market demand, and conservation status is needed.     

Global mismatches in aboveground and belowground biodiversity

Human activities are accelerating global biodiversity change and have resulted in severely threatened ecosystem services. A large proportion of terrestrial biodiversity is harbored by soil, but soil biodiversity has been omitted from many global biodiversity assessments and conservation actions, and understanding of global patterns of soil biodiversity remains limited. In particular, the extent to which hotspots and coldspots of aboveground and soil biodiversity overlap is not clear. We examined global patterns of these overlaps by mapping indices of aboveground (mammals, birds, amphibians, vascular plants) and soil (bacteria, fungi, macrofauna) biodiversity that we created using previously published data on species richness. Areas of mismatch between aboveground and soil biodiversity covered 27% of Earth's terrestrial surface. The temperate broadleaf and mixed forests biome had the highest proportion of grid cells with high aboveground biodiversity but low soil biodiversity, whereas the boreal and tundra biomes had intermediate soil biodiversity but low aboveground biodiversity. While more data on soil biodiversity are needed, both to cover geographic gaps and to include additional taxa, our results suggest that protecting aboveground biodiversity may not sufficiently reduce threats to soil biodiversity. Given the functional importance of soil biodiversity and the role of soils in human well-being, soil biodiversity should be considered further in policy agendas and conservation actions by adapting management practices to sustain soil biodiversity and considering soil biodiversity when designing protected areas.