Sense or no-sense of the sum parameter for water soluble "adsorbable organic halogens" (AOX) and "absorbed organic halogens" (AOX-S18) for the assessment of organohalogens in sludges and sediments

"AOX" is the abbreviation of the sum parameter for water soluble "adsorbable organic halogens" in which 'A' stands for adsorbable, 'O' for organic and 'X' for the halogens chlorine, bromine and iodine.After the introduction of the AOX in 1976, this parameter has been correctly used for "real" AOX constituents (DDT and its metabolites, PCBs, etc.) but also misused for non-adsorbable adsorbed OX-compounds, mostly high molecular organohalogens in plants and even to inorganic compounds being neither organic nor adsorbable.The question of natural "Adsorbable Organic Halogens" (AOX) formed by living organisms and/or during natural abiogenic processes has been definitively solved by the known existence of already more than 3650 organohalogen compounds, amongst them the highly reactive, cancerogenic vinyl chloride (VC).The extension of the AOX to AOX-S18 for Sludges and Sediments, in which A stands for adsorbed (not for adsorbable) is questionable. It includes the most important water insoluble technical organochlorine product: polyvinyl chloride, PVC.In addition to organic halogens it also includes inorganic, mineralogenic halides, incorporated mainly in the crystal lattice of fine grained phyllosilicates, the typical clay minerals (kaolinite, montmorillonite, illite and chlorite) which are main constituents of sediments and sedimentary rocks representing the major part of the sedimentary cover of the earth.Other phyllosilicates, biotite and muscovite, major constituents of granites and many metamorphic rocks (gneiss and mica schist) will also contribute to the AOX-S18 especially in soils as result of weathering processes.Since chlorine is incorporated into the mineral structure and, as a consequence, not soluble by the nitric acid analytical step (pH 0.5) of the S18 determination, it will account to the AOX-S18 in the final charcoal combustion step at temperatures >950 degrees C.After heavy rainfalls sewage sludge composition is strongly influenced by mineralogenic components derived from the erosion of fine grained sediments or soils. Assuming 50% geogenic particles with a mean Cl concentration of 103 mg/kg (as in shales and clays) the mineralogenic Cl-content could add about 50 mg/kg to the organic AOX in sewage sludge.The occurrence of insoluble and non-adsorbable PVC in sewage sludge exhibits the same problems as the mineralogenic constituents: a detection as AOX-S18 is possible when the final high temperature analytical step is applied.Plants as major sources of organohalogens have never been doubted.Only recently [Science 295 (2002) 985] based on the determination of the form of Cl with near-edge X-ray adsorption fine structure (NEXAFS) spectroscopy and extended X-ray adsorption showed the variations in the inorganic Cl(-) and organo-Cl compounds with increasing humification of plant leaves from "fresh leaves--senescent leaves on plants--senescent leaves on soil--powdered top soil--isolated soil humus". His finding of exclusively inorganic Cl(-) in the starting material (fresh leaves) is controverse to our earlier results indicating the presence of ionic inorganic Cl together with water insoluble absorbed organohalogens (AOX-S18) in eight different macrophytes of both terrestrial and marine environments.Our research on AOX in interstitial water of anaerobic limnic sediments has led to the role of bromine playing in the diagenesis of the organic matter of sediments. In sediments of Lake Constance Br(-) concentrations in lake water at the sediment water interface increased from <0.01 to 0.25 mg/l in the pore water at 77 cm sediment depth.In the Neckar River a Br concentrations of 0.02 mg/l at the water/sediment interface increasing to 0.74 mg/l in pore water in 85 cm depth was found. Here a parallel development could be found with ammonium concentration and alkalinity. The very high positive correlation ammonium:bromide and bromide:alkalinity leads to the conclusion, that bromine, originally a high molecular constituent of the organic matter, is released as bromide during an early dehalogenation stage of diagenesis.The mlusion, that bromine, originally a high molecular constituent of the organic matter, is released as bromide during an early dehalogenation stage of diagenesis.The main general reason to discard the AOX sum parameter as a whole lies in the fact, that adsorbable halogenated substances cannot a priori be categorized as natural/anthropogenic, biotic/abiotic, harmful/harmless. If applied to sludges and sediments, adsorbed organohalogens are not water soluble and therefore not adsorbable, and mineralogenic halogens (X) are neither organic nor adsorbable, and therefore by definition no AOX.     

Photochemically induced formation of the "Al13" tridecameric polycation in the presence of Fe(III) and organic acids

We found that light-induced Fe(III) reduction associated with the oxidation of a simple hydroxy-carboxylic acid (lactate) caused the formation of the AlO4Al12(OH)24(H2O)12 polycation ("Al13"). Initial conditions were a lactate:Al:Fe ratio of 1:0.76:0.11 in a partially neutralized solution. Base was added rapidly and no Al13 was detected in samples kept in the dark. With exposure to light, Fe(III) reduction was rapid and Fe(II) reached a maximum within 1 day. After the maximum, steady-state Fe(II) declined from 54% to 43% over eight days. During this same time period, the lactate concentration fell to 2% of the original, pH rose from 4.05 to 4.46, and the Al13 detectable by 27Al NMR increased to 2.3 mmol l(-1) (51% of the total solution Al). The formation of Al13 is attributed to the pH rise resulting from the removal of the organic acid buffer. Similar photo-induced chemical changes occur in natural waters and may promote the formation of Al13, conditions permitting.     

Acute toxicity of polybrominated diphenyl ethers (PBDEs) for turbot (<Emphasis Type="Italic">Psetta maxima</Emphasis>) early life stages (ELS)

Background, aim and scope  

The environmental presence of polybrominated diphenyl ethers (PBDEs), among which BDE-47 and BDE-99 are particularly abundant, makes toxicity data necessary to assess the hazard risk posed by PBDE to aquatic organisms. This study examines the effects of BDE-47 and BDE-99 on embryo-larval stages of the marine flatfish turbot.     

The three-dimensional structure of 3, 3', 5'-trichloro-4-methoxybiphenyl, a "coplanar" polychlorinated biphenyl (PCB) derivative

The crystal structure of a "coplanar" polychlorinated biphenyl (PCB) derivative, 4-methoxy-3, 3', 5'-trichlorobiphenyl (C13H9Cl3O), is described. The torsion angle of the title compound is 41.31(07) degrees, which is in good agreement with the calculated torsion angle of 38.2 degrees in aqueous solution.     

The Biological System of the Elements (BSE)--a brief introduction into historical and applied aspects with special reference on "ecotoxicological identity cards" for different element species (e.g. As and Sn)

There are different methods to estimate and predict effects of chemical elements and corresponding speciation forms in biochemistry and toxicology, including statements on essentiality and antagonisms. Two approaches are given here: (1) "identity cards" describing biologically fundamental aspects of element chemistry and (2) qualitative discussions which assume the existence of (indirect ways into) chemical autocatalysis to be essential for maintaining life and permitting reproduction. The latter method, developed by the present authors, draws upon Stoichiometric Network Analysis, a safe procedure for complexity reduction in feedback networks) and provides estimates of concentration regimes for different elements suitable for survival and reproduction. The biochemical hierarchy level considered here is that of (metallo-)proteins. Thermodynamic toxicity aspects are given in correlations with DMSO solvent affinities and thiocyanate bonding modes. Effects of antagonists and of ion substitution within metalloenzymes or of metabolic simplification can be dealt with, likewise increased sensitivities within symbiotic relationships and within carcinomas are explained which are relevant for environmental monitoring and tumour therapy, respectively.     

Chlorinated guaiacols and catechols bioaccumulation potential in bleaks (Alburnus alburnus, Pisces) and reproductive and toxic effects on the har-pacticoid Nitocra spinipes (Crustacea)

The bioaccumulation potential in bleaks (Alburnus alburnus, Pisces) and acute toxic and reproductive effects on Nitocra spinipes (Crustacea), of 4,5,6-trichloroguaiacol (I), tetrachloroguaiacol (II) and tetrachlorocatechol (III) was investigated. Continuous flow tests with I and II (10 μg/l) gave a rapid bi-phasic uptake in the fish with I and II reaching a level of 4 μg/g fresh weight after 14 d. An equally rapid excretion was determined with the detection limit of I and II being reached after 10 days in pure water. The 96-h LC50 values for I, II and III to N. spinipes was determined to 5.2, 3.9 and 3.3 mg/l, respectively, in static tests. The fecundity of N. spinipes was reduced to 50 % of the control values at 37±6 and 54±4 μg/l (II) per liter in static and continuous flow tests, respectively.     

Simultaneous conversion of CHClF(2) and CH(3)Br to CH(2)CF(2)

Gas phase reaction of CHClF(2) with CH(3)Br in an alumina tube reactor at 773-1123 K as a function of various input ratios of CH(3)Br to CHClF(2) is presented. The major products detected include C(2)F(4), CH(2)CF(2), and CH(4). Minor products include CH(3)Cl, CHF(3), C(2)H(4), C(2)H(2), CH(2)CF-CF(3), and C(2)H(3)F. The reaction produces a high yield of CH(2)CF(2) (53% based on CHClF(2) feed) at 1123 K and an input molar ratio of CH(3)Br to CHClF(2) of 1.8, suggesting that the reaction potentially can be developed as a process to convert two ozone depleting substances (CHClF(2) and CH(3)Br) to a highly valuable chemical, CH(2)CF(2). The reaction of CHClF(2) with CH(3)Cl and CH(3)I was also investigated under similar reaction conditions, to assist in understanding the reaction chemistry involved in the reaction of CHClF(2) with CH(3)Br.     

Emission halogenierter Dibenzodioxine (PXDD) und Dibenzofurane (PXDF) aus Verbrennungsmotoren beim Betrieb mit handelsüblichen Betriebsstoffen

Nach heutigem Kenntnisstand mu? bei jeder unvollst?ndigen Verbrennung, die im Beisein halogenierter Verbindungen abl?uft, mit der Entstchung von polyhalogenierten Dibenzodioxinen und Dibenzofuranen (PXDD/PXDF) gerechnet werden. Bestechenden Anzeichen, da? auch Verbrennungsmotoren diese Substanzen im Spurenbereich emittieren, mu? man Bedeutung beimessen. Da es bisher nur stichprobenartige Untersuchungen des Kfz-Verkehrs gab, hat der Bundesminister für Forschung und Technologie (BMFT) gemeinsam mit der Deutschen Wissenschaftlichen Gesellschaft für Mineral?lwirtschaft und Kohlechemie e.V. (DGMK) sowie der Forschungsvereinigung Verbrennungskraftmaschinen e.V. (FVV) zur Kl?rung dieser Frage umfangreiche Forschungsarbeiten durchführen lassen. Die Ergebnisse des seit Juli 1987 gef?rderten Verbundforschungsvorhabens “Untersuchungen zur Emission halogenierter Dibenzodioxine und Dibenzofurane aus Verbrennungsmotoren beim Betrieb mit handelsüblichen Betriebsstoffen” führten schlie?lich zu dem Entwurf einer“Verordnung über ein Verbor der Scavenger im bleihaltigen Benzin”, der z.Z. auf seine Verabschiedung wartet. Partner der Untersuchung waren das Institut für Verbrennungsmotoren und Kraftfahrwesen der Universit?t Stuttgart für den motorischen Teil, das Institut für Organische Chemie der Universit?t Tübingen und der Lehrstuhl für ?kologische Chemie und Geochemie der Universit?t Bayreuth für den analytischen Teil sowie die Deutsche Gesellschaft für Mineral?lwirtschaft und Kohlechemie e.V. für die begleitende Analytik der Mineral?lprodukte.     

Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms

Background, aim, and scope  The adverse environmental impacts of chlorinated hydrocarbons on the Earth’s ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C–F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF₃CF₂CF₂OCH₃) (1) and its isomer CF₃CF₂CF₂CH₂OH (2). Materials and methods  Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube–mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266–333 and 298–353 K for reactions of HFE-7000 and CF₃CF₂CF₂CH₂OH, respectively. Results  The measured room temperature rate constants were k(Cl+CF₃CF₂CF₂OCH₃) = (1.24 ± 0.28) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹and k(Cl+CF₃CF₂CF₂CH₂OH) = (8.35 ± 1.63) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ (errors are 2σ + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k ₁(266–333 K) = (6.1 ± 3.8) × 10⁻¹³exp[−(445 ± 186)/T] cm³ molecule⁻¹ s⁻¹ and k ₂(298–353 K) = (1.9 ± 0.7) × 10⁻¹²exp[−(244 ± 125)/T] cm³ molecule⁻¹ s⁻¹ (errors are 2σ). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 ± 0.38 and 0.97 ± 0.16 (errors are 2σ) were obtained for CF₃CF₂CF₂OCH₃ and CF₃CF₂CF₂CH₂OH, respectively. Discussion  The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k ₁ and k ₂, HFE-7000 is significantly less reactive than its isomer C₃F₇CH₂OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of –CF₂– in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of –CF₂– without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C₃H₇CH₂OH, respectively. Conclusions  The studied CFCs’ substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, τ _Cl values as low as 2.5 and 0.4 years for HFE-7000 and C₃H₇CH₂OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF₃CF₂CF₂OCH₃, significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. Recommendations and perspectives  The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure–reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.     

Comments on "Sorption of triazoles to soil and iron minerals" by Y. Jia et al. [Chemosphere 67 (2007) 250-258

This letter suggests possible improvements on the discussion of the adsorptive removal of triazoles by iron minerals which are possible corrosion products of elemental iron materials (Fe0) in a recent article by Jia et al. [Jia, Y., Aagaard, P., Breedveld, G.D., 2007. Sorption of triaxoles to soil and iron materials. Chemosphere 67, 250-258]. Also recalled is the importance of the adsorption of organics by iron corrosion products which is not properly addressed in the iron technology literature when the contaminants are redox-sensitive.     

Effect of N-hydroxyethyl-ethylenediamine-triacetic acid (HEDTA) on Cr(VI) reduction by Fe(II)

The complexation of Fe(II) with organic ligand results in the decrease of redox potential, and enhances the reduction ability of Fe(II). An important example is the use of Fe(II)-organic complexes to accelerate Cr(VI) reduction. Dissolved O(2) and light can potentially affect Cr(VI) reduction; however, these two factors have not been adequately evaluated. A batch technique was used to investigate the Cr(VI) reduction as influenced by the light and dissolved O(2) using N-hydroxyethyl-ethylenediamine-triacetic acid (HEDTA) and Fe(II) solutions. The oxidation of Fe(II) by dissolved O(2) was rapid in the presence of HEDTA at low pH; nonetheless, the oxidation proceeded slowly when HEDTA was absent. Although Cr(VI) could be reduced by free Fe(II) at low pH, the reaction was considerably slower than that of systems involving HEDTA. The enhancement of Cr(VI) reduction by Fe(II) in the presence of high concentrations of HEDTA was achieved as a result of two processes. First, HEDTA acted as a ligand for expediting electron transfer between Fe(II) and Cr(VI). Secondly, HEDTA served as a reductant for Cr(VI) under illumination.