Sequential supercritical fluid extraction (SSFE) for estimating the availability of high molecular weight polycyclic aromatic hydrocarbons in historically polluted soils

Sequential supercritical fluid (CO2) extraction (SSFE) was applied to eight historically contaminated soils from diverse sources with the aim to elucidate the sorption-desorption behavior of high molecular weight polycyclic aromatic hydrocarbons (PAHs). The method involved five extraction phases applying successively harsher conditions by increasing fluid temperature and density mobilizing target compounds from different soil particle sites. Two groups of soils were identified based on readily desorbing (available) PAH fractions obtained under mildest extraction conditions (e.g., readily desorbing fractions of fluoranthene and pyrene significantly varied between the soils ranging from <10 to >90%). Moreover, extraction behavior strongly correlated with molecular weight revealing decreasing available PAH fractions with increasing weight. Physicochemical soil parameters such as particle size distribution and organic dry mass were found to have no distinct effect on the sorption-desorption behavior of PAHs in the different soils. However, PAH profiles significantly correlated with readily available pollutant fractions; soils with relatively less mobile PAHs had higher proportions of five- and six-ring PAHs and vice versa. Eventually, biodegradability corresponded well with PAH recoveries under the two mildest extraction phases. However, a quantitative relationship was only established for soils with biodegradable PAHs. Out of eight soils, five showed no biodegradation including the four soils with the lowest fraction of readily desorbing PAHs. Only one soil (which was found to be highly toxic to Vibrio fischeri) did not match the overall pattern showing no PAH biodegradability but large fractions of highly mobile PAHs, concluding that mass transfer limitations may only be one of many factors governing biodegradability of PAHs.     

Verbleib von spurenschadstoffen bei der methylesterherstellung aus altspeisefett im technikumsmaßstab

Aims and Scope

In Germany, 120,000 tons per year of waste edible fats are collected from the catering and the food industry Until recently, these fats have widely been used as a nutritional additive for poultry and other animals fodder. Due to the BSE crisis and some affairs based on dioxins in feeding stuff, waste fats are now barely used as fodder. Currently, these fats substitute fresh vegetable oils in the chemical industry and are used as raw material for the production of biodiesel. Therefore, alternative fields of application are required. In this context, the Deutsche Bundesstiftung Umwelt (DBU) is sponsoring a joint research project which deals with the production and testing of cooling lubricants based on monoesters made from waste edible fats.

Methods

In a first step, characteristics and quality of wasteedible fats of different origins were chemically analysed and monitored. The investigations covered the following fat specific parameters: total contamination, sulphate ash, water content, peroxide number, iodine value, kinematical viscosity, neutralisation number (free fatty acids) and fatty acid spectra. In the next step, a process development/optimisation was carried out for the production of methylesters based on the raw material waste fat, leading to the construction of a pilot plant. To investigate the fate of trace pollutants during the production process of waste-fat methylester, samples were systematically contaminated with polycyclic aromatic hydrocarbons, polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and the elements Al, Cd, Cr, Cu, Ni, P, Pb, Sn, and Zn. These contaminated fat samples were transesterified in laboratory scale. The primary and by-products were analysed subsequently.

Results

Valuable hints on the design of the technical process of fatty adid methylester production based on waste edible fats were gained by regarding the fat specific parameters. For example, filtration and dewatering of the waste fats proved necessary. The saturated fatty acids, most wanted for the production of cooling lubricants due to their high oxidation stability, were present in the range of 11,3% to 31,6%. Due to the low content of free fatty acids, a base catalysed process occurred more suitable for the transesterification of the waste edible fats. Trace analytical investigations concerning inorganic and organic pollutants proved a low basic contamination of the waste edible fats. Experiments with systematic contamination of the fats indicated an accumulation of the heavy metals in the glycerol phase during the transesterification process, whereas the organic pollutants were detected in the methylester fraction by amounts of 80% to 95%.

Outlook

In a next step, the further processing of the methylesters to monoesters with alcohols of the chain length C2 to C8 will be presented. Associated results of chemical-analytical investigations on the process and the application of the cooling lubricants will also be given.     

Ambient level volatile organic compound (VOC) monitoring using solid adsorbents--recent US EPA studies

Ambient air spiked with 1-10 ppbv concentrations of 41 toxic volatile organic compounds (VOCs) listed in US Environmental Protection Agency (EPA) Compendium Method TO-14A was monitored using solid sorbents for sample collection and a Varian Saturn 2000 ion trap mass spectrometer for analysis. The adsorbent was a combination of graphitic carbon and a Carboxen-type carbon molecular sieve. The method detection limits (MDLs) for 11 samples were typically 0.5 parts per billion by volume (ppbv) and lower except for bromomethane and chloromethane, both of which exhibited breakthrough. Thirty-day sample storage on the sorbents resulted in less than a 20% change for most compounds, and water management was required for humid samples to avoid major anomalous decreases in response during analyses. The adsorbent-based system, a system using canister-based monitoring, and a semi-continuous automated GC/MS (autoGC) monitoring system with a Tenax GR/Carbotrap B/Carbosieve S-III adsorbent preconcentrator were compared using spiked ozone concentrations as a variable. In this comparison, the target compounds included a number of n-aldehydes as well as those listed in TO-14A. The effects of ozone on the TO-14A compounds were relatively minor with the exception of negative artifacts noted for styrene and 1,1,2,2-tetrachloroethane. However, a small, systematic decrease in response was evident for a number of aromatic VOCs and 1,1,2,2-tetrachloroethane when ozone was increased from 50 to 300 ppbv. Method averages for multiple runs under the same conditions were typically within +0.25 ppbv of their mean for most compounds. For n-aldehydes, strong positive artifacts using the autoGC preconcentrator and strong negative artifacts for the canister-based and carbon sorbent approaches caused major disagreement among methods. These artifacts were mostly eliminated by using MnO2 ozone scrubbers, although loss of the n-aldehydes for all methods occurred after a single sample collection of 1 h duration, apparently due to the interaction of the n-aldehydes and products of the O3, MnO2 reaction on the scrubber.     

Estimating the biogenic enhancement factor of weathering using an inverse viability method

To determine the influence of the biosphere on weathering we use a dynamic model of the global carbon cycle. It takes into account the most important processes for the long-term evolution of the Earth. The model is solved under a slowly changing environment of increasing solar luminosity and volcanic activity and continental area. By comparing the model results for the global average temperature with data derived from δ¹⁸O values from cherts it is possible to quantify the biogenic enhancement factor of weathering. For this purpose a newly developed inverse viability method is applied, which allows for calculating the range of possible biogenic enhancement factors consistent with the data. We find that in the Precambrian the weathering was 5.4 times lower than in the Phanerozoic era. This supports the hypothesis that the Cambrian explosion was caused by a positive feedback between the spread of biosphere, increased silicate weathering, and a consequent cooling of the climate.     

Testing implementation conditions for in-vehicle information systems

In the European 6th Framework Programme, fundamental research in the field of technology assessment regarding behavioural effects was conducted in the HASTE (Human machine interface And the Safety of Traffic in Europe) project. Methods, metrics and scenarios for the exploration of safety problems related to IVIS (in-vehicle information systems) were defined and applied to the evaluation of surrogate systems in the laboratory originally and real systems subsequently, in laboratories and field studies. The results of the laboratory and field studies led to the formulation of guidelines for a standardized test regime regarding existing and newly developed IVIS. In this way the HASTE project has succeeded in the development of a valid, reliable and efficient tool that may aid testing authorities in their safety evaluation of IVIS.     

Assessing effects of aerobic and anaerobic conditions on phosphorus sorption and retention capacity of water treatment residuals

Water treatment residuals (WTRs) are the by-products of drinking water clarification processes, whereby chemical flocculants such as alum or ferric chloride are added to raw water to remove suspended clay particles, organic matter and other materials and impurities. Previous studies have identified a strong phosphorus (P) fixing capacity of WTRs which has led to experimentation with their use as P-sorbing materials for controlling P discharges from agricultural and forestry land. However, the P-fixing capacity of WTRs and its capacity to retain sorbed P under anaerobic conditions have yet to be fully demonstrated, which is an issue that must be addressed for WTR field applications. This study therefore examined the capacity of WTRs to retain sorbed P and sorb further additional P from aqueous solution under both aerobic and anaerobic conditions. An innovative, low cost apparatus was constructed and successfully used to rapidly establish anoxic conditions in anaerobic treatments. The results showed that even in treatments with initial solution P concentrations set at 100 mg l(-1), soluble reactive P concentrations rapidly fell to negligible levels (due to sorption by WTRs), while total P (i.e. dissolved + particulate and colloidal P) was less than 3 mg l(-1). This equated to an added P retention rate of >98% regardless of anaerobic or aerobic status, indicating that WTRs are able to sorb and retain P in both aerobic and anaerobic conditions.