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.
Institute of Environmental Geochemistry, University of Heidelberg Im Neuenheimer Feld 236, D-69120 Heidelberg, Germany. gmueller@ugc.uniheidelberg.de
German
G
Müller
D000042:Absorption; D000327:Adsorption; D004784:Environmental Monitoring / Q000379:methods / Q000592:standards; D019015:Geologic Sediments / Q000737:chemistry*; D006846:Hydrocarbons, Halogenated / Q000032:analysis* / Q000737:chemistry / Q000378:metabolism; D010944:Plants / Q000737:chemistry; D012680:Sensitivity and Specificity; D012722:Sewage / Q000737:chemistry*; D012995:Solubility; D014865:Waste Disposal, Fluid / Q000379:methods; D014867:Water / Q000737:chemistry; D014874:Water Pollutants, Chemical / Q000032:analysis*
D006846:Hydrocarbons, Halogenated; D012722:Sewage; D014874:Water Pollutants, Chemical; D014867:Water