Chlorcarbazole in Böden

Goal and Scope

In soil samples taken from several locations throughout Bavaria, the detection of p,p′-DDT by GC/MS was impeded by a superimposed peak. The authenticity of this compound, which has been identified as dichlorocarbazole by mass spectra databases, is confirmed and some characteristics of its occurrence in soils are described.

Methods

The authenticity of the unknown compound has been checked by comparing the low resolution mass spectra and chromatographic retention times with those of standard compounds. Some methodical studies concerning extraction and clean-up were also carried out.

Results and Conclusion

Mass spectra and retention of the unknown compound are identical with that of the 3,6-dichlorocarbazole standard compound; additionally, a second chlorocarbazole was found with mass spectrum and retention similar to 3-chlorocarbazole. In many topsoils (A-horizons) and subsoils (B-horizons) from 200 locations of different land-uses, the dichlorocarbazole could be detected. In contrast to PAH and other POPs, maximum concentrations occurred in the A- and upper B-horizons of forest soils rather than in the organic layers. Assuming the environmental distribution properties of the chlorocarbazoles to be similar to those of the PAH, this could indicate that the chlorocarbazoles are not deposited from the atmosphere as a result of anthropogenic activities but might be generated by natural processes in situ.

Recommendation and Perspective

To our knowledge, the occurrence of chlorocarbazoles in soils of unpolluted sites has not been previously described. Their widespread occurrence in relatively high concentrations and their detection using analytical standard procedures is surprising and requires further examination.     

EFFECTS OF BEST MANAGEMENT PRACTICES ON FOREST STREAMWATER QUALITY IN EASTERN KENTUCKY1

ABSTRACT: Forest land managers are concerned about the effects of logging on soil erosion, streamflow, and water quality and are promoting the use of Best Management Practices (BMPs) to control impacts. To compare the effects of BMP implementation on streamwater quality, two of three small watersheds in Kentucky were harvested in 1983 and 1984, one with BMPs, the other without BMPs. There was no effect of clearcutting on stream temperatures. Streamflow increased by 17.8 cm (123 percent) on the BMP watershed during the first 17 months after cutting and by 20.6 cm (138 percent) on the Non-BMP watershed. Water yields remained significantly elevated compared to the uncut watershed 8 years after harvesting. Suspended sediment flux was 14 and 30 times higher on the BMP and Non-BMP Watersheds, respectively, than on the uncut watershed during treatment, and 4 and 6.5 times higher in the 17 months after treatment was complete. Clearcutting resulted in increased concentrations of nitrate, and other nutrients compared to the uncut watershed, and concentrations were highest on the non-BMP watershed. Recovery of biotic control over nutrient losses occurred within three years of clearcutting. The streamside buffer strip was effective in reducing the impact of clearcutting on water yield and sediment flux.     

Environmentally friendly production of thiobencarb (Bolero)

S-Alkyl thiocarbamates are commercially available and widely used for their herbicidal properties. Despite the numerous methods for synthesizing these compounds, most employ toxic reagents that are harmful to the environment. Within we report a novel efficient one-pot process for the formation of thiobencarb employing readily available reagents. This method makes use of a trichloroacetyl chloride adduct and requires no complex starting materials. Furthermore, this process is efficient, proceeds in high yields, and utilizes several recyclable reagents.     

Modelling the environmental degradation of water contaminants. Kinetics and mechanism of the riboflavin-sensitised-photooxidation of phenolic compounds

The aerobic visible-light-photosensitised irradiation of methanolic solutions of either of the phenolic-type contaminants model compounds (ArOH) p-phenylphenol (PP), p-nitrophenol (NP) and phenol (Ph), and for two additional phenolic derivatives, namely p-chlorophenol (ClP) and p-methoxyphenol (MeOP), used in some experiments, was carried out. Employing the natural pigment riboflavin (Rf) as a sensitiser, the degradation of both the ArOH and the very sensitiser was observed. A complex mechanism, common for all the ArOH studied, operates. It involves superoxide radical anion (O₂^√−) and singlet molecular oxygen (O₂(¹Δ_g)) reactions. Maintaining Rf in sensitising concentrations levels (≈0.02 mM), the mechanism is highly dependent on the concentration of the ArOH. Kinetic experiments of oxygen and substrate consumption, static fluorescence, laser flash photolysis and time-resolved phosophorescence detection of O₂(¹Δ_g) demonstrate that at ArOH concentrations in the order of 10 mM, no chemical transformation occurs due to the complete quenching of Rf singlet excited state. When ArOH is present in concentrations in the order of mM or lower, O₂^√− is generated from the corresponding Rf radical anion, which is produced by electron transfer reaction from the ArOH to triplet excited Rf. The determined reaction rate constants for this step show a fairly good correlation with the electron-donor capabilities for Ph, PP, NP, ClP and MeOP. In this context, the main oxidative species is O₂^√−, since O₂(¹Δ_g) is quenched in an exclusive physical fashion by the ArOH. The production of O₂^√− regenerates Rf impeding the total degradation of the sensitiser. This kinetic scheme could partially model the fate of ArOH in aquatic media containing natural photosensitisers, under environmental conditions.     

On-road vehicle particulate matter and gaseous emission distributions in Las Vegas, Nevada, compared with other areas

During the spring and summer of 2000, 2001, and 2002, gaseous and particulate matter (PM) fuel-based emission factors for approximately 150,000 low-tailpipe, individual vehicles in the Las Vegas, NV, area were measured via on-road remote sensing. For the gaseous pollutants (carbon monoxide, hydrocarbons, and nitrogen oxide), a commercial vehicle emissions remote sensing system (VERSS) was used. The PM emissions were determined using a Lidar-based VERSS. Emission distributions and their shapes were analyzed and compared with previous studies. The large skewness of the distributions is evident for both gaseous pollutants and PM and has important implications for emission reduction policies, because the majority of emissions are attributed to a small fraction of vehicles. Results of this Las Vegas study and studies at other geographical locations were compared. The gaseous pollutants were found to be close to those measured by VERSS in other U.S. cities. The PM emission factors for spark ignition and diesel vehicles are in the range of previous tunnel and dynamometer studies.     

A multidisciplinary study of archaeological grape seeds

We report here the first integrated investigation of both ancient DNA and proteins in archaeobotanical samples: medieval grape (Vitis vinifera L.) seeds, preserved by anoxic waterlogging, from an early medieval (seventh–eighth century A.D.) Byzantine rural settlement in the Salento area (Lecce, Italy) and a late (fourteenth–fifteenth century A.D.) medieval site in York (England). Pyrolysis gas chromatography mass spectrometry documented good carbohydrate preservation, whilst amino acid analysis revealed approximately 90% loss of the original protein content. In the York sample, mass spectrometry-based sequencing identified several degraded ancient peptides. Nuclear microsatellite locus (VVS2, VVMD5, VVMD7, ZAG62 and ZAG79) analysis permitted a tentative comparison of the genetic profiles of both the ancient samples with the modern varieties. The ability to recover microsatellite DNA has potential to improve biomolecular analysis on ancient grape seeds from archaeological contexts. Although the investigation of five microsatellite loci cannot assign the ancient samples to any geographic region or modern cultivar, the results allow speculation that the material from York was not grown locally, whilst the remains from Supersano could represent a trace of contacts with the eastern Mediterranean.