Bestimmung von Mineralölkohlenwasserstoffen in Bodenproben mit Hilfe der Dünnschichtchromatographie

A thin-layer chromatographic method for the determination of mineral oil hydrocarbons (aliphatic compounds and naphtenes) of medium and low volatility in soil samples is presented which is based on their separation and quantitative determination. The extraction of the soil samples is effected by means of an n-hexane-acetone mixture (10∶1) supported by ultrasonics. The evaluation can be made visually or densitometrically by means of a thin-layer scanner. The applicability and restrictions of the method are shown. The advantage of the method lies in its low requirements pertaining to apparatus and chemicals, as well as in its rapidness which makes it suitable for quick in-situ analyses as, for example, for the assessment of the mineral oil content of a contaminated site.     

Multicompartmental fate of persistent substances

Background, Aim and Scope Modelling of the fate of environmental chemicals can be done by relatively simple multi-media box models or using complex atmospheric transport models. It was the aim of this work to compare the results obtained for both types of models using a small set of non-ionic and non-polar or moderately polar organic chemicals, known to be distributed over long distances. Materials and Methods Predictions of multimedia exposure models of different types, namely three multimedia mass-balance box models (MBMs), two in the steady state and one in the non-steady state mode, and one non-steady state multicompartment chemistry-atmospheric transport model (MCTM), are compared for the first time. The models used are SimpleBox, Chemrange, the MPI-MBM and the MPI-MCTM. The target parameters addressed are compartmental distributions (i.e. mass fractions in the compartments), overall environmental residence time (i.e. overall persistence and eventually including other final sinks, such as loss to the deep sea) and a measure for the long-range transport potential. These are derived for atrazine, benz-[a]-pyrene, DDT, α and γ-hexachlorocyclohexane, methyl parathion and various modes of substance entry into the model world. Results and Discussion Compartmental distributions in steady state were compared. Steady state needed 2–10 years to be established in the MCTM. The highest fraction of the substances in air is predicted by the MCTM. Accordingly, the other models predict longer substance persistence in most cases. The results suggest that temperature affects the compartmental distribution more in the box models, while it is only one among many climate factors acting in the transport model. The representation of final sinks in the models, e.g. burial in the sediment, is key for model-based compartmental distribution and persistence predictions. There is a tendency of MBMs to overestimate substance sinks in air and to underestimate atmospheric transport velocity as a consequence of the neglection of the temporal and spatial variabilities of these parameters. Therefore, the long-range transport potential in air derived from MCTM simulations exceeds the one from Chemrange in most cases and least for substances which undergo slow degradation in air. Conclusions and Perspectives MBMs should be improved such as to ascertain that the significance of the atmosphere for the multicompartmental cycling is not systematically underestimated. Both types of models should be improved such as to cover degradation in air in the particle-bound state and transport via ocean currents. A detailed understanding of the deviations observed in this work and elsewhere should be gained and multimedia fate box models could then be ‘tuned in’ to match better the results of comprehensive multicompartmental transport models. ESS-Submission Editor: Prof. Dr. Michael Matthies (matthies@uos.de)     

Life cycle assessment of the waste hierarchy--a Danish case study on waste paper

The waste hierarchy is being widely discussed these days, not only by cost-benefit analysts, but a growing number of life cycle assessments (LCA) have also begun to question it. In this article, we investigate the handling of waste paper in Denmark and compare the present situation with scenarios of more waste being recycled, incinerated or consigned to landfill. The investigations are made in accordance with ISO 14040-43 and based on the newly launched methodology of consequential LCA and following the recent guidelines of the European Centre on Waste and Material Flows. The LCA concerns the Danish consumption of paper in 1999, totalling 1.2 million tons. The results of the investigation indicate that the waste hierarchy is reliable; from an environmental point of view recycling of paper is better than incineration and landfilling. For incineration, the reason for the advantage of landfilling mainly comes from the substitution of fossil fuels, when incinerators provide heat and electricity. For recycling, the advantage is related to the saved wood resources, which can be used for generating energy from wood, i.e., from renewable fuel which does not contribute to global warming.     

Automobile injury trends in the contemporary fleet: Belted occupants in frontal collisions

Objective: As vehicle safety technologies and evaluation procedures advance, it is pertinent to periodically evaluate injury trends to identify continuing and emerging priorities for intervention. This study examined detailed injury distributions and injury risk trends in belted occupants in frontal automobile collisions (10 o’clock to 2 o’clock) using NASS-CDS (1998–2015).

Methods: Injury distributions were examined by occupant age and vehicle model year (stratified at pre- and post-2009). Logistic regression models were developed to examine the effects of various factors on injury risk (by body region), controlling for delta-V, sex, age, height, body mass index (BMI), vehicle model year (again stratified at 2009).

Results: Among other observations, these analyses indicate that newer model year vehicles (model year [MY] 2009 and later) carry less risk of Abbreviated Injury Scale (AIS) 2+ and AIS 3+ injury compared to older model year vehicles, with odds ratios of 0.69 (AIS 2+) and 0.45 (AIS 3+). The largest reductions in risk between newer model year vehicles and older model year vehicles occur in the lower extremities and in the risk of skull fracture. There is no statistically significant change in risk of AIS 3+ rib fracture or sternum injury between model year categories. Females are at greater risk of AIS 2+ and AIS 3+ injury compared to males, with increased risk across most injury types.

Conclusions: For belted occupants in frontal collisions, substantial reductions in injury risk have been realized in many body regions in recent years. Risk reduction in the thorax has lagged other body regions, resulting in increasing prevalence among skeletal injuries in newer model year vehicles (especially in the elderly). Injuries also remain common in the arm and hand/wrist for all age ranges studied. These results provide insight into where advances in the field have made gains in occupant protection and what injury types remain to be addressed.     

Impact of weathered multi-walled carbon nanotubes on the epithelial cells of the intestinal tract in the freshwater grazers Lymnaea stagnalis and Rhithrogena semicolorata

Freshwater grazers are suitable organisms to investigate the fate of environmental pollutants, such as weathered multi-walled carbon nanotubes (wMWCNTs). One key process is the uptake of ingested materials into digestive or absorptive cells. To address this, we investigated the localization of wMWCNTs in the intestinal tracts of the mud snail Lymnaea stagnalis (L. stagnalis) and the mayfly Rhithrogena semicolorata (R. semicolorata). In L. stagnalis, bundles of wMWCNTs could be detected in the midgut lumen, whereas only single wMWCNTs could be detected in the lumina of the digestive gland. Intracellular uptake of wMWCNTs was detected by transmission electron microscopy (TEM) but was restricted to the cells of the digestive gland. In larvae of R. semicolorata, irritations of the microvilli and damages in the apical parts of the epithelial gut cells were detected after feeding with 1 to 10 mg/L wMWCNTs. In both models, we detected fibrillar structures in close association with the epithelial cells that formed peritrophic membranes (PMs). The PM may cause a reduced transmission of wMWCNT bundles into the epithelium by forming a filter barrier and potentially protecting the cells from the wMWCNTs. As a result, the uptake of wMWCNTs into cells is rare in mud snails and may not occur at all in mayfly larvae. In addition, we monitor physiological markers such as levels of glycogen or triglycerides and the RNA/DNA ratio. This ratio was significantly affected in L. stagnalis after 24 days with 10 mg/L wMWCNTs, but not in R. semicolorata after 28 days and 10 mg/L wMWCNTs. However, significant effects on the energy status of R. semicolorata were analysed after 28 days of exposure to 1 mg/L wMWCNTs. Furthermore, we observed a significant reduction of phagosomes per enterocyte cell in mayfly larvae at a concentration of 10 mg/L wMWCNTs (p?<?0.01).

     

Distribution and incorporation mode of the herbicide MCPA in soil derived organo-clay complexes

The incorporation of xenobiotics into soil, especially via covalent bonds or sequestration has a major influence on the environmental behavior including toxicity, mobility, and bioavailability. The incorporation mode of 4-chloro-2-methylphenoxyacetic acid (MCPA) into organo-clay complexes has been investigated under a low (8.5 mg MCPA/kg soil) and high (1000 mg MCPA/kg soil) applied concentration, during an incubation period of up to 120 days. Emphasis was laid on the elucidation of distinct covalent linkages between non-extractable MCPA residues and humic sub-fractions (humic acids, fulvic acids, and humin). The cleavage of compounds by a sequential chemical degradation procedure (OH^?, BBr₃, RuO₄, TMAH thermochemolysis) revealed for both concentration levels ester/amide bonds as the predominate incorporation modes followed by ether linkages. A possible influence of the soil microbial activity on the mode of incorporation could be observed in case of the high level samples. Structure elucidation identified MCPA as the only nonextractable substance, whereas the metabolite 4-chloro-2-methylphenol was additionally found as bioavailable and bioaccessible compound.     

Distribution, fate and formation of non-extractable residues of a nonylphenol isomer in soil with special emphasis on soil derived organo-clay complexes

Anthropogenic contaminants like nonylphenols (NP) are added to soil, for instance if sewage-sludge is used as fertilizer in agriculture. A commercial mixture of NP consists of more than 20 isomers. For our study, we used one of the predominate isomers of NP mixtures, 4-(3,5-dimethylhept-3-yl)phenol, as a representative compound. The aim was to investigate the fate and distribution of the isomer within soil and soil derived organo-clay complexes. Therefore, (14)C- and (13)C-labeled NP was added to soil samples and incubated up to 180 days. Mineralization was measured and soil samples were fractionated into sand, silt and clay; the clay fraction was further separated in humic acids, fulvic acids and humin. The organo-clay complexes pre-incubated for 90 or 180 days were re-incubated with fresh soil for 180 days, to study the potential of re-mobilization of incorporated residues. The predominate incorporation sites of the nonylphenol isomer in soil were the organo-clay complexes. After 180 days of incubation, 22 % of the applied (14)C was mineralized. The bioavailable, water extractable portion was low (9 % of applied (14)C) and remained constant during the entire incubation period, which could be explained by an incorporation/release equilibrium. Separation of organo-clay complexes, after extraction with solvents to release weakly incorporated, bioaccessible portions, showed that non-extractable residues (NER) were preferentially located in the humic acid fraction, which was regarded as an effect of the chemical composition of this fraction. Generally, 27 % of applied (14)C was incorporated into organo-clay complexes as NER, whereas 9 % of applied (14)C was bioaccessible after 180 days of incubation. The re-mobilization experiments showed on the one hand, a decrease of the bioavailability of the nonylphenol residues due to stronger incorporation, when the pre-incubation period was increased from 90 to 180 days. On the other hand, a shift of these residues from the clay fraction to other soil fractions was observed, implying a dynamic behavior of incorporated residues, which may result in bioaccessibility of the NER of nonylphenol.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) on glass surfaces

Sorption of polycyclic aromatic hydrocarbons (PAHs) to glass commonly used in laboratories was studied. Sorption coefficients (K_d) of five selected PAHs to borosilicate glass surfaces were measured using column chromatography. A linear relationship between log K_d and the corresponding water solubility of the subcooled liquid (log S_w) of the investigated PAHs was observed. Based on the determined sorption coefficients our data revealed that mass loss caused by sorption on glass walls strongly depends on the ratio of solution volume to contacted surface area (V/S). The influence of solution chemistry such as ionic strength, solution pH, presence of cosolvent, and the influence of temperature on the sorption process were investigated. In the presence of ionic strength, sorption coefficients concurrently increased but less than a factor of 2 up to 0.005 M calcium chloride concentration. However, further increasing ionic strength had no influence on K_d. The cosolvent reduced sorption at a concentration of methanol in water above 0.5% (v/v); however, for benzo[a]pyrene even with 10% (v/v) methanol the mass loss would be still higher than 10% (with a V/S ratio less than 0.25). Significant effects of the solution pH and temperature were not observed. These results suggest that van der Waal’s forces dominate the sorption process. In the analysis of highly hydrophobic PAHs in aqueous samples, mass loss due to sorption on glass walls should be accounted for in the final result if untreated glass is used. The presented relationship between log K_d and log S_w may help to decide if such a correction is necessary. Furthermore, the frequently used silanization of glass surfaces may not be sufficient to suppress sorption for large PAHs.     

Impact of Dredging on Phosphorus Transport in Agricultural Drainage Ditches of the Atlantic Coastal Plain1

Abstract: Drainage ditches can be a key conduit of phosphorus (P) between agricultural soils of the Atlantic Coastal Plain and local surface waters, including the Chesapeake Bay. This study sought to quantify the effect of a common ditch management practice, sediment dredging, on fate of P in drainage ditches. Sediments from two drainage ditches that had been monitored for seven years and had similar characteristics (flow, P loadings, sediment properties) were sampled (0‐5 cm) after one of the ditches had been dredged, which removed fine textured sediments (clay = 41%) with high organic matter content (85 g/kg) and exposed coarse textured sediments (clay = 15%) with low organic matter content (2.2 g/kg). Sediments were subjected to a three‐phase experiment (equilibrium, uptake, and release) in recirculating 10‐m‐long, 0.2‐m‐wide, and 5‐cm‐deep flumes to evaluate their role as sources and sinks of P. Under conditions of low initial P concentrations in flume water, sediments from the dredged ditch released 13 times less P to the water than did sediments from the ditch that had not been dredged, equivalent to 24 mg dissolved P. However, the sediments from the dredged ditch removed 19% less P (76 mg) from the flume water when it was spiked with dissolved P to approximate long‐term runoff concentrations. Irradiation of sediments to destroy microorganisms revealed that biological processes accounted for up to 30% of P uptake in the coarse textured sediments of the dredged ditch and 18% in the fine textured sediments of the undredged ditch. Results indicate that dredging of coastal plain drainage ditches can potentially impact the P buffering capacity of ditches draining agricultural soils with a high potential for P runoff.