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.     

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.

     

Transport impacts on atmosphere and climate: Land transport

Emissions from land transport, and from road transport in particular, have significant impacts on the atmosphere and on climate change. This assessment gives an overview of past, present and future emissions from land transport, of their impacts on the atmospheric composition and air quality, on human health and climate change and on options for mitigation.In the past vehicle exhaust emission control has successfully reduced emissions of nitrogen oxides, carbon monoxide, volatile organic compounds and particulate matter. This contributed to improved air quality and reduced health impacts in industrialised countries. In developing countries however, pollutant emissions have been growing strongly, adversely affecting many populations. In addition, ozone and particulate matter change the radiative balance and hence contribute to global warming on shorter time scales. Latest knowledge on the magnitude of land transport's impact on global warming is reviewed here.In the future, road transport's emissions of these pollutants are expected to stagnate and then decrease globally. This will then help to improve the air quality notably in developing countries. On the contrary, emissions of carbon dioxide and of halocarbons from mobile air conditioners have been globally increasing and are further expected to grow. Consequently, road transport's impact on climate is gaining in importance. The expected efficiency improvements of vehicles and the introduction of biofuels will not be sufficient to offset the expected strong growth in both, passenger and freight transportation. Technical measures could offer a significant reduction potential, but strong interventions would be needed as markets do not initiate the necessary changes. Further reductions would need a resolute expansion of low-carbon fuels, a tripling of vehicle fuel efficiency and a stagnation in absolute transport volumes. Land transport will remain a key sector in climate change mitigation during the next decades.     

A European model for waste and material flows

The use of materials and the generation of waste are linked to economic activities and in many projections these are assumed to be a constant ratio of the economic activities. This may be the case considering detailed economic activities and unchanged technology. However, the assumption of constant coefficients is questionable when linking material use and waste generation to aggregated economic activities. Therefore, in this paper, econometrics is used to test the assumption of constant waste coefficients empirically. The analyses show that an assumption of constant waste coefficients is not supported, generally, and a model allowing for trendwise changing coefficients is developed and used for projections of waste and material flows in 25 European countries.     

Comparative study of polyhydroxyalkanoates production from acidified and anaerobically treated brewery wastewater using enriched mixed microbial culture

The production of polyhydroxyalkanoates(PHA) from wastewaters using microbial mixed cultures(MMC) has been attracting increased interest because of PHA's biodegradability characteristics. Production of PHA by an MMC enriched with PHA-accumulating bacteria was compared using anaerobically treated and acidified brewery wastewaters under various feeding strategies, namely pulse and batch feed addition. To obtain an enriched MMC, a sequencing batch reactor was inoculated with activated sludge fed with acetate and subjected to aerobic dynamic feeding. The enriched MMC was able to accumulate PHA up to 72.6% of cell dry weight(CDW) with pulse addition of acetate controlled by the dissolved oxygen(DO) concentration in the reactor. In a batch accumulation experiment with acetate,the PHA content achieved(28.5% CDW) was less than that of the pulse feeding strategy with the same amount of acetate(～2000 mg C/L). Using anaerobically treated and acidified brewery wastewater fed in pulses, the maximum PHA accumulated by the enriched MMC was similar for both wastewaters(45% CDW), in spite of the higher volatile fatty acid concentration in acidified brewery wastewater. The pulse feed addition controlled by the DO concentration was difficult to implement for wastewater as compared to acetate because the difference in DO concentration between substrate availability and depletion was low. For the batch addition of acidified wastewater, a slightly lower PHA content(39%CDW) was obtained. These results show that both brewery wastewaters can be utilized for PHA production with a similar maximum PHA storage capacity.     

Time management and nectar flow: flower handling and suction feeding in long-proboscid flies (Nemestrinidae: Prosoeca)

A well-developed suction pump in the head represents an important adaptation for nectar-feeding insects, such as Hymenoptera, Lepidoptera and Diptera. This pumping organ creates a pressure gradient along the proboscis, which is responsible for nectar uptake. The extremely elongated proboscis of the genus Prosoeca (Nemestrinidae) evolved as an adaptation to feeding from long, tubular flowers. According to the functional constraint hypothesis, nectar uptake through a disproportionately elongated, straw-like proboscis increases flower handling time and consequently lowers the energy intake rate. Due to the conspicuous length variation of the proboscis of Prosoeca, individuals with longer proboscides are hypothesised to have longer handling times. To test this hypothesis, we used field video analyses of flower-visiting behaviour, detailed examinations of the suction pump morphology and correlations of proboscis length with body length and suction pump dimensions. Using a biomechanical framework described for nectar-feeding Lepidoptera in relation to proboscis length and suction pump musculature, we describe and contrast the system in long-proboscid flies. Flies with longer proboscides spent significantly more time drinking from flowers. In addition, proboscis length and body length showed a positive allometric relationship. Furthermore, adaptations of the suction pump included an allometric relationship between proboscis length and suction pump muscle volume and a combination of two pumping organs. Overall, the study gives detailed insight into the adaptations required for long-proboscid nectar feeding, and comparisons with other nectar-sucking insects allow further considerations of the evolution of the suction pump in insects with sucking mouthparts.     

Wirkung von Isoproturon auf Laich und Larven zweier Unkenarten (Bombina spec.)

In intensively used arable areas, a contamination of the reproduction ponds with pesticides probably impairs the development of spawn and tadpoles of amphibians, based on the coincidental space and time. Therefore, the effects of the herbicide isoproturon (IPU) on the early life stages of the firebellied toad (Bombina bombina) and the closely related yellowbellied toad (Bombina variegata) were investigated. The results of the exposure with¹⁴C-labelled IPU (1 μg/L) indicated an uptake into the spawn and tadpoles of bothBombina species. The jelly capsules could not protect the embryo from effects of the herbicide. Tadpoles with complete opercula and without external gills were most sensitive to contamination by IPU. Physical and behavioral abnormalities of the tadpoles developed at concentrations, of 0.1 μg/L after 24 h exposure. At increasing IPU-concentrations the number of impaired and dead tadpoles increased significantly compared to the control. The enzymatic system of the Glutathion S-Transferase (GST) of theBombina tadpoles were influenced significantly by the duration and concentration of IPU exposure. Compared to the pure active ingredient IPU, the commercial herbicide TOLKAN FLO^® provoked a stronger enzymatic response in the tadpoles. This could be caused by the presence of an emulsifier used in the TOLKAN FLO^® formulation which enhanced the availability of IPU and/or the interaction between IPU and the emulsifier.