Screening of organic halogens and identification of chlorinated benzoic acids in carbonaceous meteorites

The occurrence of halogenated organic compounds measured as a sum parameter and the evidence of chlorinated benzoic acids in four carbonaceous meteorites (Cold Bokkeveld, Murray, Murchison and Orgueil) from four independent fall events is reported. After AOX (Adsorbable organic halogen) and EOX (Extractable organic halogen) screening to quantify organically bound halogens, chlorinated organic compounds were analyzed by gas chromatography. AOX concentrations varying from 124 to 209 microg Cl/g d.w. were observed in carbonaceous meteorites. Ion chromatographic analysis of the distribution of organically bound halogens performed on the Cold Bokkeveld meteorite revealed that chlorinated and brominated organic compounds were extractable, up to 70%, whereas only trace amounts of organofluorines could be extracted. Chlorinated benzoic acids have been identified in carbonaceous meteorite extracts. Their presence and concentrations raise the question concerning the origin of halogenated, especially chlorinated, organic compounds in primitive planetary matter.     

Sorption and desorption hysteresis of organic contaminants by kerogen in a sandy aquifer material

Sorption and desorption hysteresis of 1,2-dichlorobenzene, 1,3,5-trichlorobenzene, naphthalene, and phenanthrene were investigated for the Borden aquifer material with total organic carbon of 0.021% and the isolated natural organic matter (NOM). The isolated NOM is a kerogen type of organic matter with relatively low maturation degree and contained many different types of organic matters including vitrinite particles. The modified Freundlich sorption capacities (logK^′_f and logK^′_foc) are very close for the sorption of the four solutes by the isolated NOM and the original sand, respectively. Isotherm non-linearity (n value) and hysteric behaviors are related to solute molecular properties (e.g. K_ow and molecular size). Kerogen encapsulated by inorganic matrices in the original aquifer may not be accessed fully by solutes. The larger the hydrophobic organic chemical (HOC) (hydrophobic organic contaminant) molecule is, the lower accessibility of the HOC to kerogen. This study disputes widely held hypothesis that sorption to mineral surfaces may play a major role in the overall sorption by low TOC (e.g. 0.1% by mass) geomaterials such as Borden sand. It also demonstrates the importance of the condensed NOM domain, even at very low contents, in the sorption and desorption hysteresis of HOCs in groundwater systems.     

Determination of group parameters for organically bound chlorine, bromine and iodine in precipitation

The presence of organically bound halogens in precipitation was studied by first adsorbing organics on activated carbon and then analysing the chloride, bromide and iodide formed during combustion of the carbon. A standard instrument for the group parameter AOX (adsorbable organic halogens) was used for the combustion. The halides formed were trapped in an alkaline solution and analysed by capillary zone electrophoresis. The method described enabled determination of sub-ppb concentrations of the group parameters AOCl, AOBr and AOI (adsorbable organic chlorine, bromine and iodine, respectively). Analysis of rain and snow collected at different sites in Europe showed that organochlorines were responsible for the major part of the AOX content in all samples collected. Organically bound bromine was found in sub-ppb concentrations in all of the samples, whereas organic iodine was detected in only two of the samples.     

Physico-chemical versus microbial release of c-atrazine bound residues from a loamy clay soil incubated in laboratory microcosms

A loamy clay soil containing unextractable ¹⁴C-ring labeled atrazine residues was incubated in microcosms under abiotic and biotic conditions. The mineralization activity of the soil microflora was evaluated by the release of total CO₂ and ¹⁴C0₂. After 63 days of sample incubation the total organic carbon mineralization was of 1.71%, that of ¹⁴C-residues was of 0.72% of the initial radioactivity. No direct relationship was established between the mineralization of atrazine residues and the global mineralization. The contribution of soil microorganisms in the release of ¹⁴C-residues was weak. The availability of non-extractable residues was mainly controlled by physico-chemical factors. The low value of the reextractability rate and the distribution of bound residues during the soil sample incubation shown the active role of organic matter in detoxification procedure. Ninety percent of the residues remained bound after 63 days of incubation and were thus, potentially available without biocide activity.

The fractionation of soil organic matter allowed to specify the distribution of bound residues within the organic compartments. After a long-stay of pesticides in soils, approximately 65% of bound residues were associated with humin.     

A microcosm approach to assessing the effects of earthworm inoculation and oat cover cropping on CO2 fluxes and biological properties in an amended semiarid soil

We designed a microcosm experiment to assess the influence of inoculation with Eisenia foetida earthworms and the establishment of an Avena sativa cover crop on biological (enzyme activities and labile carbon fractions) soil quality indicators in a soil treated with a composted organic residue, and to determine the contribution of these treatments to carbon dioxide emissions from the soil to the atmosphere of the microcosm. The microcosms were incubated for 53 days under 28 °C/18 °C day/night temperatures. The addition of earthworms and the planting of A. sativa increased dehydrogenase activity of compost amended soil by about 44% after 23 days of incubation. The metabolic potential, calculated as the ratio dehydrogenase activity/water soluble C, was higher in the compost amended soil planted with A. sativa. The highest total amount of CO₂–C evolved occurred in the soil treated with composted residue and earthworms (about 40% of the total amount of CO₂ evolved came from earthworm activity). The planting of A. sativa increased the decomposition rate constant of organic matter in the amended soil but decreased the potentially mineralizable C pool. In conclusion, the establishment of an A. sativa cover crop and the addition of E. foetida to a degraded agricultural soil treated with composted residue were effective treatments for improving the biological and biochemical quality and the metabolic potential of the soil.     

Fractionation of halogenated organic matter present in rain and snow

Organic matter in samples of rain and snow from Sweden, Poland, Germany and the Republic of Ireland was fractionated by employing a series of filtration, purging, evaporation and extraction steps. Determinations of the group parameter AOX (adsorbable organic halogens) in aqueous phases and EOX (extractable organic halogens) in organic phases showed that halogenated organic matter present in bulk precipitation is composed of several different groups of compounds. The largest amounts of organically bound halogens were found in fractions of relatively polar and non-volatile to semivolatile compounds. In particular, a significant part of the AOX could be attributed to alkaline-labile organic bases. Gas chromatographic analysis of different organic extracts in the chlorine channel of an atomic emission detector (AED) resulted in chromatograms with few distinct peaks, and analysis in the bromine channel did not produce any distinct peaks. Chlorinated acetic acids were the most abundant halogenated organic acids, and chlorinated alkyl phosphates were normally responsible for the largest peaks in the chlorine chromatogram of neutral, hexane-extractable compounds. When analysing volatiles, 1,4-dichlorobenzene and a thus far unidentified chloroorganic compound often caused the largest response in the chlorine channel of the AED system.     

Preparation and characteristics of high performance paper containing titanium dioxide photocatalyst supported on inorganic fiber matrix

A novel paper-based material containing titanium dioxide (TiO₂) photocatalyst was successfully prepared by a papermaking technique with the internal addition of inorganic fibers on which TiO₂ particles were supported. Photodegradation performance of acetaldehyde gas, an indoor pollutant, and the durability of the TiO₂-containing papers were investigated under UV irradiation. Ceramic fiber suspension and polydiallyldimethylammonium chloride as a cationic flocculant were mixed, followed by the addition of TiO₂ suspension and anionic polyacrylamide. Subsequently, the inorganic mixture was poured into a pulp suspension, and TiO₂ handsheets then prepared by a papermaking method. The tensile strength of TiO₂-containing paper without a ceramic carrier decreased by more than 30% after 240-h UV irradiation (2 mW/cm²), although the strength of the TiO₂ sheet with ceramic fibers remained reasonably stable. The efficiency of acetaldehyde decomposition by the TiO₂ paper containing an inorganic carrier was nearly equal to that of the carrier-free TiO₂ paper. Scanning electron microscopic observation suggested that most TiO₂ particles were predominantly supported on the inorganic fiber matrix, and were mostly out of contact with organic pulp fibers. The TiO₂ paper with an inorganic carrier demonstrated both excellent photocatalytic performance and durability, which before had been mutually incompatible for organic materials containing TiO₂ photocatalyst. The two-stage mixing procedure for TiO₂ sheet-making is promising for the simple manufacture of high performance paper with photocatalytic ability.     

Leaching of atrazine, metolachlor and diuron in the field in relation to their injection depth into a silt loam soil

A field experiment was conducted on a Calcaric Cambisol soil to study the consequences of the penetration depth and properties of pesticides on the risk of subsequent leaching. Three pesticides with different mobility characteristics and bromide were injected at 30 cm (where soil organic matter (OM) was 2%) and 80 cm (soil OM 0.5%) on irrigated plots without a crop. The migration of injected solutes was assessed for two years by sampling the soil solution using six porous cups installed at 50 and 150 cm depth and by relating solute contents to drainage water flux estimated by the STICS model (Simulateur mulTIdisciplinaire pour les Cultures Standard). Pesticides injected at 30 cm were strongly retained so that no metolachlor or diuron was detected at 50 and 150 cm. The ratio of atrazine peak concentration in the soil solution to concentration in the injected solution (C/C₀) was 1 × 10⁻³ and 0.2 × 10⁻³, respectively, at 50 and 150 cm. When injected at 80 cm, (C/C₀) of atrazine, metolachlor and diuron were 10 × 10⁻³, 1 × 10⁻³ and 0.3 × 10⁻³ at 150 cm, respectively; 1/(C/C₀) was correlated with K_oc values reported from databases. The ratio of drainage volume to the amount of water at field capacity in the soil layer between the injection point at 30 cm and the water sampling level (V/V₀) at 50 and 150 cm was 0.6 and 0.9, respectively, for bromide and 1.6 and 1.0 for atrazine. V/V₀ of the injected solutes at 80 cm was for bromide, atrazine, metolachlor and diuron 0.6, 0.9, 1.2 and 1.7, respectively; pesticide V/V₀ was correlated with K_oc. The retardation factor was a good indicator of migration risk, but tended to overestimate retardation of molecules with high K_oc. Atrazine desorption represented an additional leaching risk as a source of prolonged low contamination. The large variability in soil solution of bromide and pesticide concentrations in the horizontal plane was attributed to flow paths and clods in the tilled soil layer. This heterogeneity was assumed to channel water fluxes into restricted areas and thereby increase the risk of groundwater contamination. The methodology used in the field proves to provide consistent results.     

Effect of clay and organic matter type on the ecotoxicity of zinc and cadmium to the potworm Enchytraeus albidus

Clay and organic matter are considered as important parameters influencing bioavailability and ecotoxicity of metals in soils. As there exists a large variation in the type of clay and organic matter in field soils, the quantity of these variables alone may not be good indicators of metal bioavailability. To test this hypothesis, toxicity experiments with the potworm Enchytraeus albidus were conducted in artificial soils with three types of clay and seven types of organic matter, while the soil pH was kept constant. The 14d LC₅₀ of zinc and cadmium varied from 83.0 to 1140 mg Zn/kg D.W. and from 55.2 to 704 mg Cd/kg D.W., respectively, depending on the type of clay and organic matter that were used. Simultaneous measurements of the cation exchange capacity showed that this soil parameter is a better indicator of the bioavailability as it takes into account the type of clay and organic matter as well as other adsorption phases such as metal oxyhydroxides.     

Batch washing of cadmium from soil and sludge by a mixture of Na2S2O5 and Na2EDTA

Washing of cadmium contaminated soil and sludge using a mixture of 0.1 M Na₂S₂O₅ and 0.01 M Na₂EDTA was investigated in the batch mode. Initial Cd concentration in samples was 500 mg kg⁻¹. The sequential extraction was conducted to study of what form that Cd was removed. SPSS program version 9.01 was performed to determine what soil parameter had the greatest influence on the washing. The organic matter in soil was found to be the main factor for the washing. Soil with low organic matter would have high percentage of removing Cd. When adding more washing solution, the Cd removal efficiency was lower. The highest removal efficiency was between 67.83% and 97.3% when using a 1 g:2.5 ml soil to washing solution ratio. The predominant form of the removed Cd was exchangeable form. By contrast for the sludge, the highest Cd removal efficiency was 17.13% when using sludge in washing solution at the ratio of 1 g:7.5 ml. Most of washed Cd was in reducible form.     

Effects of SOM, surfactant and pH on the sorption-desorption and mobility of prometryne in soils

Sorption and desorption of the herbicide prometryne in two types of soil subjected to the changes of pH and soil organic matter and surfactant were investigated. The sorption and desorption isotherms were expressed by the Freundlich equation. Freundlich K_f and n values indicate that soil organic matter was the major factor affecting prometryne behavior in the test soils. We also quantified the prometryne sorption and desorption behavior in soils, which arose from the application of Triton X-100 (TX100), a nonionic surfactant and change in pH. Application of TX100 led to a general decrease in prometryne sorption to the soils and an increase in desorption from the soils when applied in dosages of the critical micella concentration (CMC) 0.5, 1 and 2. At the concentration below the CMC, the non-ionic surfactant showed a tendency to decrease prometryne sorption and desorption. It appeared that TX100 dosages above CMC were required to effectively mobilize prometryne. Results indicate that the maximum prometryne sorption and minimum prometryne desorption in soils were achieved when the solution pH was near its pK_a. Finally, the influence of TX100 on the mobility of prometryne in soils using soil thin-layer chromatography was examined.     

Organic residue decomposition: The minicontainer-system a multifunctional tool in decomposition studies

The Minicontainer-test, first described by Eisenbeis (1993), was designed to study the kinetics of organic residue decomposition at a microsite level. It is derived from the litterbag technique and consists of polyethylene minicontainers (volume about 1.5 cm³) filled with a test substrate (litter, straw, cellulose, etc.). The minicontainers (MCs) are closed at either end with plastic gauze discs of variable mesh size (e.g. 20 μm, 250 μm, 500 μm or 2 mm). A definite number of such units are inserted into PVC-bars, which can be implanted into the soil horizontally or vertically, or be exposed on the soil surface horizontally. The bars are very stable and can be exposed in different environments for months to years. If required, the bars can be removed temporarily and stored, e.g. during soil cultivation. Should fresh litter be used, two phases of decomposition can be distinguished: a fast initial phase, which can be mainly related to the effect of leaching, and a second slow phase depending mainly on the activity of soil organisms and litter quality. Several questions can be addressed to investigations using MCs, e.g. 1) parts of the soil fauna which are involved in decomposition (nematodes, microarthropods, and smaller specimens of the macrofauna, e.g. enchytraeidae, diplopods and dipteran larvae) can be extracted from the litter substrate using a miniscale high gradient extractor, 2) the organic mass loss of litter can be determined, 3) microbial biomass (C_mic, N_mic) can be assessed by fumigation extraction and 4) microbial activity (respiration) in the test substrate can also be assessed by use of standardised methods. Compared to litterbag studies, the larger number of small replicate units improves the statistical evaluation. Until today the Minicontainer-test has been applied in forestry and agriculture, e.g. studying the effects of liming, soil restoration and the application of insecticides, e.g. Diflubenzuron (Dimilin) and Btk (Bacillus thuringiensis var.kurstaki).     

Fate of arsenic compounds in poultry litter upon land application

The use of the organic As compound, roxarsone, as an antibiotic additive to poultry feed continues to raise concern over potential negative environmental impacts. Total As concentration in poultry litter can reach >40 mg kg⁻¹ and both roxarsone and its mineralization product As(V) have been identified in poultry litters (PL). To investigate the fate of these As species upon land application of PL we conducted two studies. In the first, an Orangeburg soil (Ultisol from the Atlantic Coastal Plain) was spiked with either 20 mg kg⁻¹ As(V) or roxarsone and incubated at 10% moisture content for 4 months. Exchangeable As was determined periodically by extraction with 0.1 M PO₄. Both As(V) and roxarsone displayed similar desorption; initially, approximately 70% of added As was ligand exchangeable and this decreased to 35% after 4 months incubation, presumably due to either slow sorption reactions or a change in solid phase speciation of As to less exchangeable forms. In the second study, various manipulations of two PL samples were applied to the Orangeburg soil at realistic field application rates. The treatments were wet to 10% moisture content and water soluble As, Cu and organic carbon (DOC) was measured over 30 days. Arsenic and Cu solubility were highest from the dried litter samples. Ashing of the PLs decreased soluble As and Cu, presumably because of the loss of organic matter from the ashed litter and subsequent decrease in DOC. Application of leachates from either PL resulted in higher concentrations of soluble As and Cu than when the soil was amended with equivalent concentrations of soluble As and Cu dissolved in DI H₂O. We hypothesize that the increased levels of DOC from the PL treatments enhance As and Cu solubility through competitive sorption and complexation, respectively. In fact, As and Cu solubility was correlated to DOC levels in the amended soil extracts. Even though land application of PL introduced relatively low concentrations of As and Cu to soil it appeared that other soluble constituents of PL significantly enhanced As and Cu solubility.     

Invertebrates control metal/metalloid sequestration and the quality of DOC/DON released during litter decay in slightly acidic environments

Plant litter and organic sediments are a main sink for metals and metalloids in aquatic ecosystems. The effect of invertebrate shredder (a key species in litter decay) on metal/metalloid fixation by organic matter is described only under alkaline water conditions whereas for slightly acidic waters nothing can be found. Furthermore, less is known about the effect of invertebrate shredders on the quality of dissolved organic carbon (DOC) and nitrogen (DON) released during litter decay. We conducted an experiment to investigate the impact of invertebrate shredder (Gammarus pulex) on metal/metalloid fixation/remobilization and on the quality of DOC/DON released under slightly acidic water conditions. During decomposition of leaf litter, invertebrate shredder facilitated significantly the emergence of smaller particle sizes of organic matter. The capacity of metal fixation was significantly higher in smaller particles (POM 2,000?C63???m) compared to original leaf litter and litter residues. Thus, G. pulex enhanced metal fixation by organic partition of sediments by increasing the amount of smaller particle of organic matter in aquatic ecosystems. In contrast, the capacity of metal/metalloid fixation in the smallest fraction of POM (<63???m) was lower compared with leaf residues in treatment without invertebrates. Remobilization of metals and metalloids was very low for all measured elements. A significant effect of invertebrates on quantitative formation of DOC/DON was confirmed. The quality of released DOC/DON, which may affect metal/metalloid remobilization, was also significantly affected by invertebrate shredders (e.g., more carboxylates). Hence, invertebrate shredder enhanced significantly the fixation of metals/metalloids into POM in slightly acidic environments.     

Determination of trichloroacetic acid in environmental studies using carbon 14 and chlorine 36

Radioisotopes carbon 14 and chlorine 36 were used to elucidate the environmental role of trichloroacetic acid (TCA) formerly taken to be a herbicide and a secondary air pollutant with phytotoxic effects. However, use of ¹⁴C-labeling posed again known analytical problems, especially in TCA extraction from the sample matrix. Therefore—after evaluation of available methods—a new procedure using decarboxylation of [1,2-¹⁴C]TCA combined with extraction of the resultant ¹⁴C-chloroform with a non-polar solvent and its subsequent radiometric measurement was developed. The method solves previous difficulties and permits an easy determination of amounts between 0.4 and 20 kBq (10–500 ng g⁻¹) of carrier-less [1,2-¹⁴C]TCA in samples from environmental investigations. The procedure is, however, not suitable for direct [³⁶Cl]TCA determination in chlorination studies with ³⁶Cl. Because TCA might be microbially degraded in soil during extraction and sample storage and its extraction from soil or needles is never complete, the decarboxylation method—i.e. 2 h TCA decomposition to chloroform and CO₂ in aqueous solution or suspension in closed vial at 90 °C and pH 4.6 with subsequent CHCl₃ extraction—is recommended here, estimated V < 7%. Moreover, the influence of pH and temperature on the decarboxylation of TCA in aqueous solution was studied in a broad range and its environmental relevance is shown in the case of TCA decarboxylation in spruce needles which takes place also at ambient temperatures and might amount more than 10–20% after a growing season. A study of TCA distribution in spruce needles after below-ground uptake shows the highest uptake rate into current needles which have, however, a lower TCA content than older needle-year classes, TCA biodegradation in forest soil leads predominatingly to CO₂.     

Metal/metalloid fixation by litter during decomposition affected by silicon availability during plant growth

Organic matter is known to accumulate high amounts of metals/metalloids, enhanced during the process of decomposition by heterotrophic biofilms (with high fixation capacity for metals/metalloids). The colonization by microbes and the decay rate of the organic matter depends on different litter properties. Main litter properties affecting the decomposition of organic matter such as the nutrient ratios and the content of cellulose, lignin and phenols are currently described to be changed by silicon availability. But less is known about the impact of silicon availability during plant growth on elemental fixation during decay. Hence, this research focuses on the impact of silicon availability during plant growth on fixation of 42 elements during litter decay, by controlling the litter properties. The results of this experiment are a significantly higher metal/metalloid accumulation during decomposition of plant litter grown under low silicon availability. This may be explained by the altered litter properties (mainly nutrient content) affecting the microbial decomposition of the litter, the microbial growth on the litter and possibly by the silicon double layer, which is evident in leaf litter with high silicon content and reduces the binding sites for metals/metalloids. Furthermore, this silicon double layer may also reduce the growing biofilm by reducing the availability of carbon compounds at the litter surface and has to be elucidated in further research. Hence, low silicon availability during plant growth enhances the metal/metalloid accumulation into plant litter during aquatic decomposition.     

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.     

The variations of aluminium species in mountainous forest soils and its implications to soil acidification

Aluminium (Al) speciation is a characteristic that can be used as a tool for describing the soil acidification process. The question that was answered is how tree species (beech vs spruce) and type of soil horizon affect Al speciation. Our hypotesis is that spruce and beech forest vegetation are able to modify the chemical characteristics of organic horizon, hence the content of Al species. Moreover, these characteristics are seasonally dependent. To answer these questions, a detailed chromatographic speciation of Al in forest soils under contrasting tree species was performed. The Jizera Mountains area (Czech Republic) was chosen as a representative mountainous soil ecosystem. A basic forestry survey was performed on the investigated area. Soil and precipitation samples (throughfall, stemflow) were collected under both beech and spruce stands at monthly intervals from April to November during the years 2008–2011. Total aluminium content and Al speciation, pH, and dissolved organic carbon were determined in aqueous soil extracts and in precipitation samples. We found that the most important factors affecting the chemistry of soils, hence content of the Al species, are soil horizons and vegetation cover. pH strongly affects the amount of Al species under both forests. Fermentation (F) and humified (H) organic horizons contain a higher content of water extractable Al and Al³⁺ compared to organo-mineral (A) and mineral horizons (B). With increasing soil profile depth, the amount of water extractable Al, Al³⁺ and moisture decreases. The prevailing water-extractable species of Al in all studied soils and profiles under both spruce and beech forests were organically bound monovalent Al species. Distinct seasonal variations in organic and mineral soil horizons were found under both spruce and beech forests. Maximum concentrations of water-extractable Al and Al³⁺ were determined in the summer, and the lowest in spring.     

Physicochemical soil parameters affecting sequestration and mycobacterial biodegradation of polycyclic aromatic hydrocarbons in soil

Six soils, obtained from grasslands and wooded areas in Northeastern Illinois, were physicochemically characterized. Measured parameters included total organic carbon (TOC) content, contents of humic acid, fulvic acid and humin, pore volume and pore size distribution, and chemical makeup of soil organic matter (determined using solid-state ¹³C-NMR). Moistened, gamma-sterilized soils were spiked with 200 ppm of either phenanthrene or pyrene (including ¹⁴C label); following 0, 40, or 120 days of aging, the contaminant-spiked soils were then inoculated with Mycobacterium austroafricanum strain GTI-23, and evolution of ¹⁴CO₂ was assessed over a 28-day period. Results for both phenanthrene and pyrene indicated that increased contact time led to increased sequestration and reduced biodegradation, and that TOC content was the most important parameter governing these processes. One soil, although only tested with phenanthrene, showed significantly lower-than-expected sequestration (higher-than-expected mineralization) after 40 days of aging, despite a very high TOC value (>24%). Because the level of sequestration in this soil was proportional to the others after 120 days of aging, this implies some difference in the temporal progression of sequestration in this soil, although not in its final result. The primary distinguishing feature of this soil was its considerably elevated fulvic acid content. Further experiments showed that addition of exogenous fulvic acid to a soil with very low endogenous humic acids/fulvic acids content greatly enhanced pyrene mineralization by M. austroafricanum. Extractabilities of 13 three- to six-ring coal tar PAHs in n-butanol from the six soils after 120 days of sequestration were strongly TOC-dependent; however, there was no discernible correlation between n-butanol extractability and mycobacterial PAH mineralization.     

Formation of methyl mercury in an aquatic macrophyte

In the nature, inorganic forms of mercury (Hg) may be transformed to the organic, very toxic, methyl-Hg. Occasionally methyl-Hg has been detected in plants, also so in the aquatic macrophyte water spinach (Ipomoea aquatica), which is a popular vegetable in tropical regions. The objectives of this study were to investigate if methyl-Hg is formed and/or degraded in water spinach. Water spinach plants were exposed to inorganic Hg via spiked soil or spiked nutrient solution. Tests were performed in a climate chamber and in experimental units, one for each individual plant, that were equipped with separated shoot and root compartments. Plant tissues were analysed for total- and methyl-Hg. The results showed that methyl-Hg was accumulated in water spinach, especially in young metabolically active parts, when exposed to external inorganic Hg, even at sterilized conditions. Results also showed that methyl-Hg was formed in water spinach in the absence of external Hg, i.e., during recovery in a not Hg-spiked medium following after HgCl₂-exposure. There was however, no sign of demethylation. Summarizing, most of the Hg that is taken up by the plants is bound in the roots, but of the comparatively small amounts of Hg that reach the young growing shoots, a part will be methylated. Since the young shoots of this plant make a delicious and very appreciated vegetable, Hg in I. aquatica may contribute to human health problems.