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.     

Assimilation,inter-organ transfer and excretion of americium in two teleost fish

Radiotracer experiments were performed (February–April, 1982) to study the assimilation and metabolism of the transuranium nuclide americium-241 in the marine teleosts Serranus scriba (Linnaeus, 1758) and Scorpaena notata Rafinesque, 1810, caught off the Monaco coast. Fish fed with ²⁴¹Am-labelled food showed that assimilation of this radionuclide takes place through the gastrointestinal walls and that the small fraction accumulated is incorporated mainly in the skin, muscle and skeleton. Gut-transfer coefficients were similar in both species and averaged 0.7% (range 0.1 to 1.7%) of the ingested activity. The calculated biological half-lives for loss of the absorbed fraction ranged between 49 and 61 d for Serranus scriba and 12 and 117 d for Scorpaena notata. Results from an intramuscular injection experiment indicated that ²⁴¹Am was retained mainly in the liver, skin and skeleton; the fraction accumulated by muscle was very low. Liver displayed a relatively short biological half-time for ²⁴¹Am loss of roughly 24 d. Routes of ²⁴¹Am excretion from the teleosts appear to be through the kidneys, gills and feces with bile serving as a possible excretion route from the liver. From the limited amount of published information available for comparison, experimental evidence is presented which suggests that ²⁴¹Am taken up via the food chain is more biologically available to marine fish than is plutonium.     

Advanced oxidation processes in azo dye wastewater treatment.

The chemical degradation of synthetic azo dyes color index (C.I.) Acid Orange 7, C.I. Direct Orange 39, and C.I. Mordant Yellow 10 has been studied by the following advanced oxidation processes: Fenton, Fenton-like, ozonation, peroxone without or with addition of solid particles, zeolites HY, and NH4ZSM5. Spectrophotometric (UV/visible light spectrum) and total organic carbon measurements were used for determination of process efficiency and reaction kinetics. The degradation rates are evaluated by determining their rate constants. The different hydroxyl radical generation processes were comparatively studied, and the most efficient experimental conditions for the degradation of organic azo dyes solutions were determined.     

Effect of copper in the protistan community of activated sludge

Protists have proved to be an interesting tool for assessing the occurrence of pollution in wastewater treatment systems along with its role in the control of pollution itself through grazing of dispersed bacteria and maintenance of a healthy trophic web in those artificial ecosystems. Two sets of assays were carried on in a bench scale pilot plant in order to study the response of the activated sludge community of protists to the exposure of copper: the first set was carried on with synthetic sewage and the second one with real sewage. The results emphasize the ability of activated sludge biological communities to survive and to react to toxicants and highlight the role of protistan communities as indicators of toxicants entrance in treatment systems.     

Six interaction profiles for simple mixtures

The Agency for Toxic Substances and Disease Registry (ATSDR) has a program for chemical mixtures that encompasses research on chemical mixtures toxicity, health risk assessment, and development of innovative computational methods. ATSDR prepared a guidance document that instructs users on how to conduct health risk assessment on chemical mixtures (Guidance Manual for the Assessment of Joint Toxic Action of Chemical Mixtures). ATSDR also developed six interaction profiles for chemical mixtures. Two profiles were developed for persistent environmental chemicals that are often found in contaminated fish and also can be detected in human breast milk. The mixture included chlorinated dibenzo-p-dioxins, hexachlorobenzene, dichlorodiphenyl dichloroethane, methyl mercury, and polychlorinated biphenyls. Two profiles each were developed for mixtures of metals and mixtures of volatile organic chemicals (VOCs) that are frequently found at hazardous waste sites. The two metal profiles dealt with (a) lead, manganese, zinc, and copper; and (b) arsenic, cadmium, chromium, and lead; the two VOCs mixtures dealt with (a) 1,1,1-trichloroethane, 1,1-dichloroethane, trichloroethylene, and tetrachloroethylene; and (b) benzene, ethylbenzene, toluene, and xylenes (BTEX). Weight-of-evidence methodology was used to assess the joint toxic action for most of the mixtures. Physiologically based pharmacokinetic modeling was used for BTEX. In most cases, a target-organ toxicity dose modification of the hazard index approach is recommended for conducting exposure-based assessments of noncancer health hazards.     

Fluid flow and solute transport in a network of channels

A new model to describe flow and transort in fractured rocks is proposed. It is based on the concept of a network of channels. The individual channel members are given stochastically selected conductances and volumes. Flow-rate calculations have been performed. For large standard deviations in conductances, channeling becomes pronounced with most of the water flowing in a few paths. The effluent patterns and flow-rate distributions obtained in the simulations have been compared to three field measurements in drifts and tunnels of flow-rate distributions. Standard deviations of channel conductances were between 1.6 and 2.4 in some cases. A particle-following technique was used to simulate solute transport in the network. Non-sorbing as well as sorbing solute transport can be simulated. By using a special technique, solutes that diffuse into the rock matrix can also be simulated.     

Persistent organochlorine compounds in soils and sediments of European high altitude mountain lakes

The composition of persistent organochlorine compounds (OC) in soils and sediments from two high altitude European mountain lakes, Redon in the Pyrenees and Ladove in the Tatra mountains, has been studied. Sediment cores from two additional lakes in the Tatra mountains, Starolesnianske Pleso and Dlugi Staw, have also been examined. DDTs (1.7-13 ng g(-1)) were the most abundant OC in soils followed by total polychlorobiphenyls (PCBs; 0.41-1.5 ng g(-1)) and hexachlorobenzene (HCB; 0.15-0.91 ng g(-1)). In sediments, the dominant OC were also DDTs (3.3-28 ng g(-1)) and PCBs (2.3-15 ng g(-1)). These concentrations are low, involving absence of major pollution sources in these high mountain regions. The downcore OC profiles in soils and sediments were similar but higher concentrations and steeper vertical gradients were observed in the latter. Radiometric determinations showed absence of significant OC transport from catchment to lake. The sediment-soil difference points therefore to a better retention of the OC load in sediments than soils which may be related to the low temperatures that are currently encountered at the bottom of the lake water column and the depletion of sediment bioturbation in these cold environments. Significant qualitative changes in the soil PCB distributions are observed downcore. These involve a dominance of the high molecular weight congeners in the top core sections and those of lower weight (i.e. less chlorinated) in the bottom. Anaerobic dechlorination of higher molecular weight congeners occurring in microsites, e.g. as observed in flooded or poorly drained soils, could be responsible for these changes. This process could be concurrent to bioturbation.     

Macrobenthic community in the Douro estuary: relations with trace metals and natural sediment characteristics

The relationship between macrobenthic community structure and natural characteristics of sediment and trace metal contamination were studied in the lower Douro estuary (Portugal, NW, Iberian Peninsula), using an innovative threefold approach (SQG, Sediment Quality Guidelines), metal normalization to Fe, and macrobenthic community structure. This study allowed detection of a clear signature of anthropogenic contamination, in terms of Zn, Cu, Pb, and Cr in the north bank of the estuary, which experiences high urban pressure. Using the SQG approach, metal concentrations above ERM (effects range-median) were observed only at one sampling station, but several stations had levels above ERL (effects range-low). The macrobenthic community had a low diversity, with only 19 species found in the entire estuarine area, dominated by opportunistic species. The granulometric distribution of the sediments (estimated from the combination of organic matter, Fe and Al) seemed to be the major structuring factor for the communities, establishing the natural macrobenthic distribution pattern. The metals (Zn, Cu, Pb, and Cr) seemed to act as a disturbing factor over the natural distribution, with deleterious consequences for the macrobenthic communities.     

The effect of cyclic aerobic-anoxic conditions on biodegradation of benzoate.

The response of a mixed microbial culture to cyclic aerobic and anoxic (denitrifying) conditions was studied in a chemostat with a 48-hour hydraulic residence time receiving a feed containing benzoate and pyruvate. When the cyclic conditions were 3-hour aerobic and 9-hour anoxic, the bacteria-degraded benzoate aerobically via the catechol 2,3-dioxygenase (C23DO) pathway. The quantity of C23DO remained constant throughout the anoxic period but decreased during the initial portion of the aerobic period before returning to the level present in the anoxic period. Anoxic biodegradation of benzoate was via benzoyl-CoA reductase, which remained constant regardless of the redox condition. The aerobic benzoate uptake capability (AeBUC) of the culture increased during the aerobic period but decreased during the anoxic period. The anoxic benzoate uptake capability (AnBUC) exhibited the opposite response. When the cycle was 6-hour aerobic and 6-hour anoxic, aerobic biodegradation of benzoate proceeded via the protocatechuate 4,5-dioxygenase (P45DO) pathway. The P45DO activity decreased early in the aerobic period, but then increased to the level present during the anoxic period. The level of benzoyl-CoA reductase was constant throughout the cycle. Furthermore, AeBUC and AnBUC responded in much the same way as in the 3/9-hour chemostat. During a 9-hour aerobic and 3-hour anoxic cycle, the culture synthesized both P45DO and C23DO, with the former having significantly higher activity. Unlike the other two cycles, AeBUC changed little during the aerobic period, although AnBUC decreased. The culture was well-adapted to the cyclic conditions as evidenced by the lack of accumulation of either substrate during any cycle tested. This suggests that cyclic aerobic-anoxic processes can be used in industrial wastewater-treatment facilities receiving significant quantities of simple aromatic compounds like benzoate. However, the results showed that the kinetics of benzoate degradation were different under aerobic and anoxic conditions, a situation that must be considered when modeling cyclic bioreactors receiving aromatic compounds.     

Surfactant solubilization of hydrophobic compounds in soil and water

The soil/water partition coefficient (K_d) of hexachlorobenzene (HCB) ranged from 220 1/kg to 1800 1/kg for eight soils having a wide range of physico-chemical properties. K_d normalised to soil organic carbon (K_oc) was found to be 28000 ± 4800 1/kg. Anionic surfactant dodecylsulphate (DS) present at concentrations above the critical micellar concentration (CMC) caused reductions in the apparent soil/water partition coefficient (K_d ^*) in the range of 3–26 times for most soils and up to 36–91 times for sandy soils. Below CMC, at environmentally relevant surfactant concentrations, K_d ^* was reduced by a factor of 1–13. For clay and calcareous soils significant adsorption/complexation/precipitation of DS occurred. At the lowest DS concentration this produced a two-fold increase in K_d ^*. At increasing DS concentrations this effect was shielded by the solubihzing effect from DS. Monomer (K_mn) and micellar (K_mc) surfactant/water partition coefficients for HCB were determined to be, 980 ± 190 1/kg and 21000 ± 1600 1/kg, respectively.