Influences of thermal decontamination on mercury removal, soil properties, and repartitioning of coexisting heavy metals

Thermal treatment is a useful tool to remove Hg from contaminated soils. However, thermal treatment may greatly alter the soil properties and cause the coexisting contaminants, especially trace metals, to transform and repartition. The metal repartitioning may increase the difficulty in the subsequent process of a treatment train approach. In this study, three Hg-contaminated soils were thermally treated to evaluate the effects of treating temperature and duration on Hg removal. Thermogravimetric analysis was performed to project the suitable heating parameters for subsequent bench-scale fixed-bed operation. Results showed that thermal decontamination at temperature >400 °C successfully lowered the Hg content to <20 mg kg⁻¹. The organic carbon content decreased by 0.06-0.11% and the change in soil particle size was less significant, even when the soils were thermally treated to 550 °C. Soil clay minerals such as kaolinite were shown to be decomposed. Aggregates were observed on the surface of soil particles after the treatment. The heavy metals tended to transform into acid-extractable, organic-matter bound, and residual forms from the Fe/Mn oxide bound form. These results suggest that thermal treatment may markedly influence the effectiveness of subsequent decontamination methods, such as acid washing or solvent extraction.     

Sorption, desorption, and degradation of (4-chloro-2-methylphenoxy)acetic acid in representative soils of the Danubian Lowland, Slovakia

Herbicide leaching through soil into groundwater greatly depends upon sorption-desorption and degradation phenomena. Batch adsorption, desorption and degradation experiments were performed with acidic herbicide MCPA and three soil types collected from their respective soil horizons. MCPA was found to be weakly sorbed by the soils with Freundlich coefficient values ranging from 0.37 to 1.03 mg^1−1/n kg⁻¹ L^1/n. It was shown that MCPA sorption positively correlated with soil organic carbon content, humic and fulvic acid carbon contents, and negatively with soil pH. The importance of soil organic matter in MCPA sorption by soils was also confirmed by performing sorption experiments after soil organic matter removal. MCPA sorption in these treated soils decreased by 37-100% compared to the original soils. A relatively large part of the sorbed MCPA was released from soils into aqueous solution after four successive desorption steps, although some hysteresis occurred during desorption of MCPA from all soils. Both sorption and desorption were depth-dependent, the A soil horizons exhibited higher retention capacity of the herbicide than B or C soil horizons. Generally, MCPA sorption decreased in the presence of phosphate and low molecular weight organic acids. Degradation of MCPA was faster in the A soil horizons than the corresponding B or C soil horizons with half-life values ranging from 4.9 to 9.6 d in topsoils and from 11.6 to 23.4 d in subsoils.     

Effect of incineration on the removal of key offensive odorants released from a landfill leachate treatment station (LLTS)

As a basic means to control odorants released from a landfill leachate treatment station (LLTS), effluents venting from this station were treated via incineration with methane rich landfill gas (at 750 °C). A list of the key offensive odorants covering 22 chemicals was measured by collecting those gas samples both before and after the treatment. Upon incineration, the concentration levels of most odorants decreased drastically below threshold levels. The sum of odorant intensities (SOIs), if compared between before and after incineration, decreased from 6.94 (intolerable level) to 3.45 (distinct level). The results indicate that the thermal incineration method can be used as a highly efficient tool to remove most common odorants (e.g., reduced sulfur species), while it is not so for certain volatile species (e.g., carbonyls, fatty acids, etc.).     

PESTICIDE RESIDUES IN THERMAL MINERAL WATER IN GREECE

Eight different hot springs (SPA) in Greece were monitored over a one-year survey for priority pesticide residues. A specific and effective procedure including solid phase extraction in combination with HPLC and GC analytical methods were applied. Samples that were sensitive to nitrogen-phosphorus (NPD) and/or electron capture (ECD) detectors were analysed by capillary gas chromatography.

From the twenty-six water samples, pesticide residues were detected in fourteen of them (54%) but no one exceeding the European Union Maximum Acceptable Concentration (MAC).

Lindane (γ-BHC) was the most frequently detected pesticide. It was found in nine samples (35%) in concentrations from <0.005 to 0.01 μg/L. Other pesticides detected were phorate (in five samples), propachlor (in two samples) and chlorpyriphos ethyl (in three samples) but in concentrations far below the permissible levels.     

Resuspension of contaminated field and formulated reference sediments Part I: Evaluation of metal release under controlled laboratory conditions

In aquatic systems where metal contaminated sediments are present, the potential exists for metals to be released to the water column when sediment resuspension occurs. The release and partitioning behavior of sediment-bound heavy metals is not well understood during resuspension events. In this study, the release of Cd, Cu, Hg, Ni, Pb and Zn from sediments during resuspension was evaluated using reference sediments with known physical and chemical properties. Sediment treatments with varying quantities of acid volatile sulfide (AVS), total organic carbon (TOC), and different grain size distributions were resuspended under controlled conditions to evaluate their respective effects on dissolved metal concentrations. AVS had the greatest effect on limiting release of dissolved metals, followed by grain size and TOC. Predictions of dissolved concentrations of Cd, Ni, Pb and Zn were developed based on the formulated sediment Σ_metal/AVS ratios with Σ_metal being the total sediment metal concentration. Predicted values were compared to measured dissolved metal concentrations in contaminated field sediments resuspended under identical operating conditions. Metal concentrations released from the field sediments were low overall, in most cases lower than predicted values, reflecting the importance of other binding phases. Overall, results indicate that for sulfidic sediments, low levels of the study metals are released to the dissolved phase during short-term resuspension.     

Desorption Kinetics of Benzene in a Sandy Soil in the Presence of Powdered Activated Carbon

Desorption kinetics of benzene was investigated with a modified biphasic desorption model in a sandy soil with five different powdered activated carbon (PAC) contents (0, 1, 2, 5, 10% w/w) as sorbents. Sorption experiments followed by series dilution desorption were conducted for each sorbent. Desorption of benzene was successively performed at two stages using deionized water and hexane. Modeling was performed on both desorption isotherm and desorption rate for water-induced desorption to elucidate the presence of sorption–desorption hysteresis and biphasic desorption and if present to quantify the desorption-resistant fraction (q _irr) and labile fraction (F) of desorption site responsible for rapid process. Desorption isotherms revealed that sorption–desorption exhibited a severe hysteresis with a significant fraction of benzene being irreversibly adsorbed onto both pure sand and PAC, and that desorption-resistant fraction (q _irr) increased with PAC content. Desorption kinetic modeling showed that desorption of benzene was biphasic with much higher (4–40 times) rate constant for rapid process (k ₁) than that for slow process (k ₂), and that the difference in the rate constant increased with PAC content. The labile fraction (F) of desorption site showed a decreasing tendency with PAC. The experimental results would provide valuable information on remediation methods for soils and groundwater contaminated with BTEX.     

Effect of salinity and sediment characteristics on the sorption and desorption of perfluorooctane sulfonate at sediment-water interface

This study investigated the influence of solution salinity, pH and the sediment characteristics on the sorption and desorption of perfluorooctane sulfonate (PFOS). The results showed that the sorption of PFOS onto sediment increased by a factor of 3 as the CaCl₂ concentration increased from 0.005 to 0.5 mol L⁻¹ at pH 7.0, and nearly 6 at pH 8.0. Desorption hysteresis occurred over all salinity. The thermodynamic index of irreversibility (TII) values increased with increasing concentration of CaCl₂. Maximum irreversibility was found in the sorption systems with CaCl₂ in the concentration of 0.5 mol L⁻¹. The results suggested that PFOS can be largely removed from the water with increasing salinity, and get trapped onto sediments irreversibly. These phenomena could be explained by salting-out effect and Ca-bridging effect. Studies also suggested that the content of total organic carbon is the dominant psychochemical properties of sediment controlling the sorption of PFOS.     

Bioaccumulation and bioavailability of polybrominated diphynel ethers (PBDEs) in soil

Earthworms were exposed to artificially contaminated soils of DE-71 and DE-79 to investigate the bioaccumulation and bioavailability of PBDEs in soil. All major congeners were bioavailable to earthworms. The uptake and elimination rate coefficients of PBDEs decreased with their logK_ows. The biota soil accumulation factors of PBDEs also declined with logK_ow. These may be due to the large molecular size and the high affinity of PBDEs to soil particles. The concentrations extracted by Tenax for 6 h correlated very well with those found in earthworms, suggesting that the bioavailability of PBDEs in soil is related to the fraction of rapid desorption from soil. This also indicates that 6 h Tenax extraction is a good proxy for the bioavailability of PBDEs to earthworms in soil. The BSAFs of PBDEs in aged soil decreased 22-84% compared to freshly spiked soil, indicating that aging may diminish the bioavailability of PBDEs in soil significantly.     

Influence of pyrene combination state in soils on its treatment efficiency by Fenton oxidation

Interactions of hydrophobic organic compounds (HOCs) with soil organic matter (SOM) determine their combination state in soils, and therefore strongly influence their mobility, bioavailability, and chemical reactivity. Contact time (aging) of an HOC in soil also strongly influences its combination state and environmental fate. We studied Fenton oxidation of pyrene in three different soils to reveal the influences of SOM, contact time, and combination state on the efficiency of vigorous chemical reactions. Pyrene degradation efficiency depended strongly on the dose of oxidant (H(2)O(2)) and catalyst (Fe(2+)); the greatest degradation was achieved at an oxidant to catalyst molar ratio of 10:1. Pyrene degradation differed among the three soils, ranging from 65.4% to 88.9%. Pyrene degradation efficiency decreased with increasing SOM content, and the aromatic carbon content in SOM was the key parameter. We hypothesize that pyrene molecules that combine with the compact net structure of aromatic SOM are less accessible to Fenton oxidation. Furthermore, pyrene degradation efficiency decreased considerably after aged for 30 days, but further aging to 60 and 180 days did not significantly change degradation efficiency. The Fenton oxidation efficiency of pyrene in both unaged and aged soils was greater than the corresponding desorption rate during the same period, perhaps because Fenton reaction can make pyrene more accessible to the oxidant through the enhancement of HOCs' desorption by generating reductant species or by destroying SOM through oxidation.     

Improving anaerobic sewage sludge digestion by implementation of a hyper-thermophilic prehydrolysis step

The present study focuses on a two-step process for treatment and stabilisation of primary sludge. The process consists of a hyper-thermophilic hydrolysis step operated at 70 degrees C and a hydraulic retention time (HRT) of 2 days followed by a thermophilic (55 degrees C) anaerobic digestion step at a HRT of 13 days. A one-step anaerobic digester operated at 55 degrees C and 15 days HRT was used as a reference process. The two-step process was characterized by a 12% higher organic suspended solids removal efficiency and better pathogen reduction effect than the conventional one-step digestion. The microbial community of the digester fed with pre-treated sludge was characterised by a higher activity compared to that of the digester treating raw sludge. Moreover, the pre-treatment of the primary sludge resulted up to 48% increase of the methane potential (20.09 and 13.56mmolCH(4)g(-)VS(-1) with and without pre-treatment, respectively) and up to 115% increase of the methane production rate. Finally it was shown that the extra energy requirements for the operation of a pre-treatment step would be covered by the energy produced from the extra methane production and in addition there would be a significant energy surplus of 2.17kJd(-1) for the system tested.