Measurement of biologically available organic material in intertidal sediments subject to inputs of sea coal or colliery wastes

A method for the measurement of biologically available organic matter in intertidal or subtidal marine sediments subject to an input of sea coal or colliery wastes is described. The method involves boiling sediment in hydrogen peroxide (H2O2) for 4 h at 160 degrees C to dissolve non-colliery waste organic matter which is then recorded as weight lost after rinsing and drying. Samples are then ashed at 495 degrees C to determine the weight of coal or colliery wastes present. Although H2O2 shows a slight reaction with colliery wastes (overall mean of 0.86% weight loss), it is appropriate to use this technique for the determination of organic matter available to sediment-dwelling biota. We show that shore organic content should not be determined merely by ashing sediment, even on shores which do not appear to contain wastes, since even visibly 'clean' shores in north-east England generally contain some coal fragments in their sediment. Our method is suitable anywhere where biologically available organic matter needs to be measured independently of waste content, e.g. in terrestrial systems close to centres of mining activity.     

Degradation of carbon tetrachloride in the presence of iron and sulphur containing compounds

The effect of several sulphur compounds: sodium sulphate, sodium sulphide, ferrous sulphide,pyrite and an organosulphonic acid on the kinetics of the iron (Fe °) induced degradation of carbon tetrachloride was examined under aerobic conditions. It was observed that all of the sulphur compounds investigated significantly accelerated the reaction. The mechanisms of the processes studied as well as their possible influence on the efficiency of the iron-induced dehalogenation of pollutants, both in situ and in above-ground treatment are discussed.     

Use of O2 consumption and CO2 production in kinetic cells to delineate pyrite oxidation-carbonate buffering and microbial respiration in unsaturated media

Identifying zones of sulphide oxidation and carbonate buffering is important in the development of a management plan for mine waste-rock piles. In this study, we used a kinetic cell technique to measure rates of O2 consumption and CO2 production in low sulphide (<0.12 wt.% S), low inorganic carbon (<0.20 wt.% C(inorganic)), gneissic waste rock and associated organic-rich lake sediment (0.7 wt.% C(organic)), and forest soil (1.4 wt.% C(organic)) collected from the Key Lake uranium mine in Saskatchewan, Canada. Solid chemistry, stable carbon isotope, pore water sulphate concentration data, and stoichiometric considerations indicated that O2 consumption and CO2 production were constrained by microbial respiration in the lake sediment and forest soil and by pyrite oxidation-carbonate buffering in the gneissic waste rock. Mean ratios of molar CO2 production to O2 consumption rates were 0.5 for lake sediment, 0.7 for forest soil, and 0.2 for gneissic waste rock. The different O2/CO2 ratios suggested that O2-CO2 monitoring may provide a practical tool for identifying the zones of microbial respiration and pyrite oxidation-carbonate buffering in mine waste-rock piles. Rates of O2 consumption and CO2 production were about one order of magnitude greater in lake sediment than in gneissic waste rock, indicating that microbial respiration would exert a control on the distribution of O2 and CO2 gas in waste-rock piles constructed upon the dewatered lake sediments.     

Aging and temperature effects on DOC and elemental release from a metal contaminated soil

The combined effect of time and temperature on elemental release and speciation from a metal contaminated soil (Master Old Site, MOS) was investigated. The soil was equilibrated at 10, 28, 45, 70 and 90 degrees C for 2 days, 2 weeks, and 2 months in the laboratory. Dissolved organic carbon (DOC), total soluble elements (by ICP), and labile metals (by DPASV) were determined in the filtered (0.22 microm) supernatants. For the samples equilibrated at 90 degrees C, DOC fractions were size fractionated by filtration and centrifugation; a subsample was only centrifuged while another was also filtered through a 0.45 microm filter. Analyses of the supernatants (ICP, DPASV, DOC) were performed on all size fraction subsamples. Dissolved organic carbon (DOC) increased both with temperature and incubation time; however, metal behavior was not as uniform. In general, total soluble metal release (ICP) paralleled the behavior of DOC, increasing with both time and temperature, and confirming the importance of soil organic matter (SOM) in metal retention. Voltammetric analysis (dpasv) of Cu and Zn showed that very little of these metals remains labile in solution due, presumably, to complexation with dissolved organic matter. Labile concentrations of Cd, on the other hand, constituted a significant portion (50%) of total soluble Cd. Copper and Al increased in solution with time (up to 2 months) and temperature up to 70 degrees C; however, at 90 degrees C the soluble concentration declined sharply. The same behavior was observed after equilibration for longer periods of time (550 days) at lower temperatures (23 and 70 degrees C). While concentrations of labile Cu and total soluble Cu and Al increased in the unfiltered samples, the trend remained the same. DPASV analysis showing shifts in labile Cu complexes with temperature and time, together with the results from the unfiltered samples, lead to the hypothesis that Cu was complexing with large polymers that could form at the elevated temperature, and thus be removed from the analyzed solution. It is possible that Cu and Al released by SOM oxidation has re-sorbed or complexed to more recalcitrant organic matter or to mineral phases. Variations in the relative molecular size fractions present within the DOC pool produced by increased time and temperature may influence the element-DOC complexes present in solution and their behavior in soil environments.     

Sulphur isotopic investigation of a polluted raised bog and the uptake of pollutant sulphur by Sphagnum

The sulphur content and sulphur isotopic composition of Sphagnum as well as anionic compositions and sulphur isotope ratios of rainwater inputs and bog waters have been measured at Thorne Moors, a raised bog in eastern England. Rainwater sulphate isotopic composition shows the sulphur input at this site to be dominated by anthropogenic pollution from fossil fuel burning. Strong depletion of sulphate (low SO4(2-)/Cl-) and enrichment in 34S in sulphate occurs at depth in the bog porewaters due to bacterial sulphate reduction. Some surface waters have low SO4(2-)/Cl-) and are 34S enriched due to removal of sulphate by downward diffusion into a sulphate-reducing zone. Other sites have high SO4(2-)/Cl-) which appears to result from oxidation of organically bound sulphur in the peat. Sulphur is present in Sphagnum at around 0.2% by weight and is depleted by 0 to -9 per thousand in the heavier 34S isotope compared to sulphate. Comparison with similar data from pristine coastal sites shows that sulphur incorporation into Sphagnum is enhanced in the polluted site (as Sphagnum sulphur concentrations are higher at lower total sulphur inputs) and that sulphur incorporation is accompanied by a smaller isotopic shift than in the pristine sites. The data support a model of preferential incorporation of partially reduced sulphur species (probably HSO3-) into Sphagnum. In pristine sites these are only available as oxidation products of sulphide formed by sulphate reduction and are 32S depleted. In polluted sites this source is augmented by sulphur(IV) species in atmospheric inputs and the resultant mixture is less depleted in 32S. Thus, in the polluted sites more HSO3- is available for uptake and the isotopic shift between Sphagnum and aqueous sulphur species is smaller.     

Humic acids from oxidized coals I. Elemental composition, titration curves, heavy metals in HA samples, nuclear magnetic resonance spectra of HAs and infrared spectroscopy

The formation of humic acids (HAs) from bituminous coal was verified by laboratory oxidation. In a relatively short time the oxidation by air at temperature above 150 degrees C led to the formation of HAs. These HAs were compared with those isolated from oxidized bituminous coal from the vicinity of red bed bodies, from weathered bituminous coal, oxihumolite and lignite. For this the organic and inorganic elemental composition of HAs, apparent dissociation constants, metal-binding capacities, nuclear magnetic resonance and infrared spectra were determined and evaluated. With increasing temperature of laboratory oxidation of bituminous coal the percentage of aromaticity of HAs increases. HAs prepared from coal oxidized at 150 degrees C are characterized by an aromaticity index 78% while for HAs prepared at 250 and 300 degrees C by 95% aromaticity. The same index for HAs isolated from naturally oxidized bituminous coals is of about 87% whereas it is of about 50% for oxihumolite and lignite. The apparent dissociation constants (Kapp) are much higher in HAs isolated from oxihumolite and lignite (pKapp from 3.35 to 3.80) than those from oxidized bituminous coal samples (pKapp from 4.47 to 4.85). There is a good negative correlation between Pb-binding capacity and pKapp of all samples suggesting that metallic ions are bonded to acidic groups of HAs. Also contents of inorganic elements like Fe, Al, Si are much higher in HAs isolated from lignite and oxihumolite than those in HAs from oxidized bituminous coal. Thus, it seems that the temperatures below 150 degrees C and the long oxidation time are necessary conditions for the formation of HAs in oxidative altered bituminous coal deposited deeply under the earth surface.     

Alkaline hydrothermal treatment of brominated high impact polystyrene (HIPS-Br) for bromine and bromine-free plastic recovery

A method to recover both Br and Br-free plastic from brominated flame retardant high impact polystyrene (HIPS-Br) was proposed. HIPS-Br containing 15% Br was treated in autoclave at 280 degrees C using water or KOH solution of various amounts and concentrations. Hydrothermal treatment (30 ml water) leads to 90% debromination of 1g HIPS-Br but plastic is strongly degraded and could not be recovered. Alkaline hydrothermal treatment (45 ml or 60 ml KOH 1M) showed similar debromination for up to 12 g HIPS-Br and plastic was recovered as pellets with molecular weight distribution close to that of the initial material. Debromination occurs at melt plastic/KOH solution interface when liquid/vapour equilibrium is attained inside autoclave (280 degrees C and 7 MPa in our experimental conditions) and depends on the plastic amount/KOH volume ratio. The antimony oxide synergist from HIPS-Br remains in recovered plastic during treatment. A pictorial imagination of the proposed debromination process is presented.     

Effects of ionic strength and temperature on adsorption of atrazine by a heat treated kerolite

The adsorption of 6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine (atrazine) on a heat treated kerolite sample at 600 degrees C (K-600) from pure water solution at 10 degrees C, 25 degrees C and 40 degrees C has been studied. The influence of the presence of 0.1 M KCl in the medium was also investigated for a better understanding of variables affecting the adsorption of this herbicide. The experimental adsorption data points were fitted to the Langmuir equation in order to calculate the adsorption capacities (Xm) of the samples; Xm values range from 2.3x10(3) mg kg-1 (pure water solution at 40 degrees C) up to 15.2x10(3) mg kg-1 (0.1 M KCl solution at 10 degrees C). The adsorption data were also fitted to the Freundlich equation in order to clarify the influence of the presence of 0.1 M KCl on atrazine adsorption. The parameter K10 obtained from this equation (adsorption capacity at an equilibrium solution concentration of atrazine equal to 10 mg l-1) shows clearly that the presence of 0.1 M KCl in the medium tends to increase the adsorption of atrazine in the range of temperature studied. The adsorption experiment also showed that the lower temperature, the more effective the adsorption of atrazine from both, pure water and 0.1 M KCl solutions. The values of the removal efficiency (R) obtained ranged from 39% at 40 degrees C (pure water solution) up to 93% at 10 degrees C (0.1 M KCl solution).     

Temperature activated degradation (mineralization) of 4-chloro-3-methyl phenol by Fenton's reagent

With the aim to evaluate the effect of temperature, 4-chloro-3-methyl phenol (CMP) degradation by Fenton's reagent was investigated at 25 and 70 degrees C under the following initial conditions: [CMP]0 = 10 mM, [Fe2+]0 = 0.5 mM; ([H2O2]0/[CMP]0) = 80, pH0 = 3. The results indicated that CMP degradation was strongly influenced by temperature. In fact, the maximum TOC removal, achieved after ca. 24h, was by far greater at 70 degrees C (85%) than at 25 degrees C (36%). The same happened for organic chlorine (TOX) conversion into inorganic chloride, i.e. 100%, after 3 h at 70 degrees C, and 87%, after 27 h at 25 degrees C. As the recorded trends of CMP removal and chloride formation were basically the same, hydroxy substitution (ipso-substitution) was hypothesised as one likely mechanism of CMP degradation. The higher level of mineralization recorded at 70 degrees C was ascribed to: (i) a greater *OH concentration; (ii) a consequently greater extent of CMP oxidation to organic acids; (iii) a higher decarboxylation rate of such acids. An interesting consequence of such extended organic acids decarboxylation was a pH increase up to 8 that, in turn, caused, in the treated mixture, the decomposition of excess H2O2 as well as the precipitation of iron ions. These two latter outcomes are technologically important considering that usually, before discharging Fenton treated wastewater, specific polishing steps are required just to remove iron ions, decompose excess hydrogen peroxide and neutralise the pH.     

Waste management of a microemulsion using elevated temperatures

Elevated temperatures reduced NAPL-saturated fraction of a treated SPME waste effluent. As temperature increased, aqueous fraction of the separated SPME increased to 0.96 at 90°C. Composite volume samples had optimal separation at 75°C, where >95% of NAPL mass partitioned into the organic phase; while in first pore volume samples, it decreased with increasing temperature after 70°C. Increasing temperature of composite volume samples increased surfactant partitioning into the organic phase; in first pore volume samples, it was evenly divided into both phases. Increased temperatures reduced COD of aqueous phases >75%. Overall, elevated temperatures reduced volume of NAPL-saturated solution by 96%.     

Atmospheric deposition and canopy exchange processes in heathland ecosystems

The aims of the present study were to determine canopy exchange processes and to quantify total atmospheric deposition of sulphur and nitrogen in heathland. The study was carried out in dry inland heath vegetation, dominated by Calluna vulgaris, in two nature reserves in the eastern part of the Netherlands. Atmospheric deposition was determined with throughfall-stemflow measurements, adapted for low vegetation. Throughflow measurements (sum of throughfall and stemflow) in artificial Calluna canopies showed co-deposition of SOx and NHy upon heathland vegetation. In the real Calluna canopy, a significant part of the deposited ammonia/ammonium was directly assimilated by the Calluna shoots, especially in wet periods. The concentrations of potassium, calcium and magnesium in throughflow, after passage through the Calluna canopy, increased significantly compared with bulk precipitation. The amount of cations lost from the canopy were in good agreement with the observed ammonium uptake by the Calluna. A field experiment demonstrated that losses of the above-mentioned cations can be doubled by application of ammonium sulphate. It was shown that interception deposition is an important component of the atmospheric deposition of sulphur and nitrogen upon Calluna heathland; bulk precipitation amounted to only c. 35-40% of total atmospheric input. Total atmospheric deposition of sulphur and nitrogen in the investigated heathlands was 1.5-2.1 (27-33 kg S ha(-1) yr(-1)) and 2.1-3.1 kmolc ha(-1) yr(-1) (30-45 kg N ha(-1) yr(-1)), respectively. It is concluded that the present atmospheric nitrogen deposition is a continuous threat for the existence of heathlands in Western Europe.     

Effects of temperature and water content on degradation of isoproturon in three soil profiles

The phenylurea herbicide isoproturon, 3-(4-isopropylphenyl)-1,1-dimethylurea (IPU), is widely used to control pre- and post-emergence of grass and broad-leaved weeds in cereal crops. Its degradation in soils is a key process for assessing its leaching risk to groundwater resources. The degradation properties of various samples from surface and subsurface soil (down to 1m depth) of a heterogeneous agricultural field were studied using (14)C-IPU. Laboratory incubations were carried out at 22 and 10 degrees C and at water contents 90% and 50% of the estimated water holding capacity (eWHC) corresponding to water potentials between -56 kPa and -660 MPa. Degradation was found to be more sensitive to water content variations than to temperature variations in the ranges that we used. For surface layers, at 10 and 22 degrees C, the degradation half-life increased by a factor 10 and 15, respectively, when water content decreased from 90% to 50% eWHC. Under optimal degradation conditions (i.e. 22 degrees C and 90% eWHC), 3-(4-isopropylphenyl)-1-methylurea (MDIPU) was the main metabolite in surface samples. At subsurface depths, IPU half-lives were larger than 100 d, IPU was the main compound after 92 d of incubation and the main metabolite was an unidentified polar metabolite. These results suggest a metabolic pathway involving hydroxylations for subsurface materials. IPU degradation was largely affected by water availability in both surface and subsurface horizons. Clay content seemed to play a major role in degradation processes in subsurface soil by determining through sorption IPU availability in soil solution and/or by limiting water availability for microorganisms.     

Lactate oxidation in pyrite suspension: a Fenton-like process in situ generating H2O2

Pyrite is a common mineral at many mining sites. In this study, the mineral pyrite was studied as a Fenton-like reagent for environmental concerns. We selected lactate as a model target molecule to evaluate the Fenton-like catalytic efficiency of pyrite upon organic oxidation. A complete set of control experiments in both aerobic and anaerobic atmospheres unequivocally established that the pyrite in aqueous solution could spontaneously in situ generate OH and H₂O₂, serving as a Fenton-like reagent to catalyze the oxidation of lactate to pyruvate with no need for additional H₂O₂. We called it the pyrite-only Fenton-like (PF) reagent. Monitoring concentration changes of lactate and pyruvate with the time indicated that the pyrite mediated the favorable pyruvate formation at pH 4.5, 60 °C, under air atmosphere. The PF reaction could be stimulated by visible light illumination. Under the optimum conditions, up to 50% of lactate was degraded within 10 d. The results suggest that pyrite and its Fenton-like processes may be potentially practical in wastewater treatment.     

A study on the environmental degradation of pesticides azinphos methyl and parathion methyl

The effect of environmental parameters (temperature and relative humidity) on the degradation rate of azinphos methyl and parathion methyl was studied. Proprietary emulsifiable concentrates were diluted and added to each of 90 glass Petri dishes for each pesticide and were left overnight to dry. Petri dishes were placed in 18 air-tight containers (9 for each pesticide) in which were created environments with relative humidity (RH) of 60, 82, and 96%. The containers were stored at 0, 20, and 40 degrees C. From the experimental results best fit curves, kinetic equations, rate constants, and half-lives were calculated. Half-lives of azinphos methyl for the RH studied were, from 124 to 267 days at 0 degrees C, from 89 to 231 days at 20 degrees C, and from 25 to 71 days at 40 degrees C. Corresponding half-lives for parathion methyl were from 48 to 57 days at 0 degrees C, from 9.2 to 10.5 days at 20 degrees C and from 1.3 to 1.5 days at 40 degrees C. The results were correlated with relevant results from the decomposition of the same or similar pesticides on apples both, on the trees and during refrigerated storage. These correlations are suggesting that biological factors strongly affected the decomposition rate of azinphos methyl. On the contrary the decomposition of parathion methyl was mainly affected by environmental rather than biological factors.     

Verification of the "first flush" phenomenon in mine water from coal mines in the Upper Silesian Coal Basin, Poland

Case studies of Grodziec and Siersza mines in the Upper Silesian Coal Basin confirm that mine water accumulating in and over-flowing from abandoned coal mines is subject to a "first flush" phenomenon. The accumulated products of sulphide oxidation are dissolved in the rising mine water and flushed out at concentrations several times those observed during mine operation. Following the first overflow, sulphate concentration and hydrogen ion activity decay exponentially. In the case of workings in Siersza, decay constants of -0.003 to -0.005 day(-1) are observed, corresponding to flushing times of 480 to 820 days, some 10-20 times the period required for the workings to flood. Quantities of leachable sulphur in the abandoned workings of 0.02-0.03% are adequate to explain the observed concentrations of sulphate in the first flush, and this figure is tentatively supported by laboratory analyses.     

Oak leaves as accumulators of airborne elements in an area with geochemical and geothermal anomalies

The Colline Metallifere (Tuscany) was a major Italian mining district (FeS2, Ag, Cu, Pb, Zn) for centuries, and in the last fifty years it has become the most important area for the exploitation of geothermal resources. Leaves of the widespread oak Quercus pubescens and surface soils were collected from 90 sampling sites in the area and their elemental composition was compared. The results showed that the composition of oak leaves was not significantly affected by the presence of mineral deposits (metal sulphide ores) or soils with high concentrations of Cr, Mg, and Ni (ultramafic). Arsenic was the only element showing higher concentrations in leaves from sites with deposits of metal sulphide ores or As-polluted soils around abandoned smelting plants. Compared to the composition of epiphytic lichens andepigeic mosses from the same sites in the Colline Metallifere, the elemental composition of Q. pubescens leaves was less affected by element contributions from adsorbed soil particles. It was thus easier to evaluate atmospheric inputs of elements in oak leaves than in cryptogams.     

Enhancement of biodegradation of oil adsorbed on fine soils in a bioslurry reactor

Techniques for enhancing the biodegradation of oil-contaminated fine soils in a slurry-phase bioreactor were investigated. Using a model system consisting of kaolin particles containing adsorbed n-dodecane as a diesel fuel surrogate, we investigated how increasing the temperature and adding a surfactant and various hydrophobic support media affected the biodegradation rate of n-dodecane. Increasing the temperature from 25 to 35 degrees C decreased the time required for complete degradation of n-dodecane by 30%, from 110h to 80h. Addition of the surfactant polyethylene glycol p-1,1,3,3-tetramethylbutylphenyl ether decreased the degradation time to less than 48h at 35 degrees C, although a high concentration of the surfactant (3000mgl(-1)) was required. We suspect that the surfactant increased the degradation rate by solubilizing the n-dodecane into the solution phase in which the microorganisms were suspended. We tested five types of organic polymers as support media for the microorganisms and found that the biodegradation time could be reduced by approximately 50% with a support medium made from polyurethane; in the presence of this medium, only 36h was required for complete decomposition at 35 degrees C. The reduction in the degradation time was probably due to transfer of the n-dodecane from the soil to the support medium, which improved contact between the n-dodecane and the microorganisms. The polyurethane support medium bearing the microorganisms was stable and could be reused.     

NaNO(2)/FeCl(3) catalyzed wet oxidation of the azo dye Acid Orange 7

A combination of ferric chloride and sodium nitrite significantly improved the wet oxidation of the azo dye Acid Orange 7 (AO7) in acid aqueous media (pH 2.6) under moderate conditions (T=150 degrees C; oxygen pressure=0.5 MPa). To evaluate the catalytic system, wet oxidation of AO7 was carried out at temperatures between 90 and 150 degrees C and oxygen pressures ranging from 0.1 to 0.5 MPa. The effect of initial solution pH from 2.6 to 11.4 and the amount of catalyst on the degradation of AO7 were also investigated. AO7 initial concentration was kept 200 mg L(-1). The degradation process was monitored by UV-visible spectroscopy, HPLC, IC (ion chromatography), GC-MS and TOC analysis. At 150 degrees C and 0.5 MPa oxygen pressure, 56% TOC was removed after 4h of treatment, while no obvious TOC removal were achieved without catalyst at the same experimental condition. The main degradation products were some small organic acids: formic acid, acetic acid, pyruvic acid, oxalic acid, succinic acid (identified and quantified by IC) and phthalic acid (identified by GC-MS).     

Inflammatory stress response in A549 cells as a result of exposure to coal: Evidence for the role of pyrite in coal workers’ pneumoconiosis pathogenesis

On the basis of a recent epidemiological study it is hypothesized that pyrite content in coal is an important factor in coal workers’ pneumoconiosis (CWP) pathogenesis. While the role of pyrite in pathogenesis remains to be resolved, the ability of the mineral to generate reactive oxygen species (ROS) through various mechanisms is likely a contributing factor. The aim of this study was to elucidate the importance of the pyrite content of coal in generating an inflammatory stress response (ISR), which is defined as the upregulation of ROS normalized by cell viability. The ISR of A549 human lung epithelial cells in the presence of natural coal samples with variable pyrite contents was measured. Normalized to surface area, five particle loadings for each coal reference standard were analyzed systematically for a total of 24 h. The ISR generated by coals containing 0.00, 0.01, and 0.49 wt.% pyritic sulfur is comparable to,though less than, the ISR generated by inert glass beads (299% of the control). The coals containing 0.52 and 1.15 wt.% pyritic sulfur generated the greatest ISR (798% and 1426% of the control, respectively).     

Efficient dehalogenation of automobile shredder residue in NaOH/ethylene glycol using a ball mill

We investigated the effectiveness of sodium hydroxide/ethylene glycol (NaOH/EG) for dehalogenation of automobile shredder residue (ASR) using a ball mill. Efficient dehalogenation was achieved at atmospheric pressure by combining the use of EG (196 degrees C b.p.) as a replacement solvent for NaOH with ball milling, which improved contact between ASR and OH(-) in solution. Moderate NaOH concentrations and increased ball mill rotation speeds produced high dechlorination that was not significantly affected by the weight ratio of ASR to EG. NaOH/EG dechlorination increased with temperature with an apparent activation energy of 50 kJ mol(-1) confirming that the reaction proceeded under chemical reaction control. The modified shrinking-core model was appropriate to explain the dechlorination process. Low chloro levels in our NaOH/EG-treated ASR suggested that this material could be used for feedstock recycling and the wet process may be applicable for dehalogenation of other important waste streams.