Destruction of PAHS from soil by using pressurized hot water extraction coupled with supercritical water oxidation

Chemical processes utilizing water both as extraction solvent and reaction medium are promising "Green Chemistry" alternatives to conventional techniques. Equipment for on-line coupled hot water extraction and supercritical water oxidation was constructed to extract polyaromatic hydrocarbons and toluene from sea sand followed by oxidation using hydrogen peroxide. The effectiveness of the technique is based on the physico-chemical properties of heated and pressurized water. Extraction efficiency increased with temperature and time; the best results were obtained at 300 degrees C with 40 min extraction time. In the oxidation stage, conversion of the PAHs increased with reaction time and oxidant concentration and the best conversion (97.0-99.9%, depending on the compound) was obtained at 425 degrees C with 43 s reaction time. Benzaldehyde and benzoic acid were the most abundant reaction intermediates in the oxidation process. In addition, phenol, p-cresol, and benzyl alcohol were found as intermediates. The intermediates originated mainly from toluene, which was present in much greater concentration than PAHs in the reaction medium.     

Fate of bisphenol A during treatment with the litter-decomposing fungi Stropharia rugosoannulata and Stropharia coronilla

Bisphenol A is an endocrine disrupting compound, which is ubiquitous in the environment due to its wide use in plastic and resin production. Seven day old cultures of the litter-decomposing fungus Stropharia coronilla removed the estrogenic activity of bisphenol A (BPA) rapidly and enduringly. Treatment of BPA with purified neutral manganese peroxidase (MnP) from this fungus also resulted in 100% reduction of estrogenic activity, as analyzed using a bioluminescent yeast assay, and in the formation of polymeric compounds. In cultures of Stropharia rugosoannulata, estrogenic activity also quickly disappeared but temporarily re-emerged in the further course of cultivation. LC-MS analysis of the extracted estrogenic culture liquid revealed [M−H]⁻ ions with m/z values of 219 and 235. We hypothesize that these compounds are ring fission products of BPA, which still exhibit one intact hydroxyphenyl group to interact with estrogen receptors displayed by the yeast.     

Review of state of the art methods for measuring water in landfills

In recent years several types of sensors and measurement techniques have been developed for measuring the moisture content, water saturation, or the volumetric water content of landfilled wastes. In this work, we review several of the most promising techniques. The basic principles behind each technique are discussed and field applications of the techniques are presented, including cost estimates. For several sensors, previously unpublished data are given. Neutron probes, electrical resistivity (impedance) sensors, time domain reflectometry (TDR) sensors, and the partitioning gas tracer technique (PGTT) were field tested with results compared to gravimetric measurements or estimates of the volumetric water content or moisture content. Neutron probes were not able to accurately measure the volumetric water content, but could track changes in moisture conditions. Electrical resistivity and TDR sensors tended to provide biased estimates, with instrument-determined moisture contents larger than independent estimates. While the PGTT resulted in relatively accurate measurements, electrical resistivity and TDR sensors provide more rapid results and are better suited for tracking infiltration fronts. Fiber optic sensors and electrical resistivity tomography hold promise for measuring water distributions in situ, particularly during infiltration events, but have not been tested with independent measurements to quantify their accuracy. Additional work is recommended to advance the development of some of these instruments and to acquire an improved understanding of liquid movement in landfills by application of the most promising techniques in the field.     

Strain-related physiological and behavioral effects of <Emphasis Type="Italic">Skeletonema marinoi</Emphasis> on three common planktonic copepods

Three strains of the chain-forming diatom Skeletonema marinoi, differing in their production of polyunsaturated aldehydes (PUA) and nutritional food components, were used in experiments on feeding, egg production, hatching success, pellet production, and behavior of three common planktonic copepods: Acartia tonsa, Pseudocalanus elongatus, and Temora longicornis. The three different diatom strains (9B, 1G, and 7J) induced widely different effects on Acartia tonsa physiology, and the 9B strain induced different effects for the three copepods. In contrast, different strains induced no or small alterations in the distribution, swimming behavior, and turning frequency of the copepods. 22:6(n-3) fatty acid (DHA) and sterol content of the diet typically showed a positive effect on either egg production (A. tonsa) or hatching success (P. elongatus), while other measured compounds (PUA, other long-chain polyunsaturated fatty acids) of the algae had no obvious effects. Our results demonstrate that differences between strains of a given diatom species can generate effects on copepod physiology, which are as large as those induced by different algae species or groups. This emphasizes the need to identify the specific characteristics of local diatoms together with the interacting effects of different mineral, biochemical, and toxic compounds and their potential implications on different copepod species.     

The application of a simplified method to map the aerobic acetate mineralization rates at the groundwater table of the Netherlands

A simplified method is used to assess the microbial activity of subsoils and soils across a broad geographic scale. Acetate was selected because it is a major intermediate in catabolic biochemical pathways. In order to get minimal disturbance, only a small amount of tritium labelled acetate and water is added to the subsoil material. After an incubation time, the subsoil material is separated from the water by centrifugation and the formed tritium labelled water is separated from the remaining acetate by evaporation. The data of 128 locations in the Netherlands were plotted in a soil map and were also compared with the depth, dry weight, electric conductivity, pH and nitrate concentration. The peat areas consisted of limed meadows with a high groundwater level whereas the sand areas often showed deeper groundwater levels and a lower pH. The subsoils at the groundwater table of the peat areas, which are in contact with soil air, showed a higher mineralization rate compared with the surface soils in our study. In contrast, the mineralization rate of the subsoil at the groundwater table of sandy soils showed on average a factor 30 lower rate. Nevertheless, the self purification capacity of the subsoil can be vital under weather conditions where the surface soil becomes less active.     

A chemical and toxicological profile of Dutch North Sea surface sediments

Chemical and toxicological profiles were assessed in surface sediments (fraction <63 μm) from the southern North Sea. In extracts of freeze-dried samples, polybrominated biphenyl (PBB), Irgarol 1051 and phthalate concentrations were below the respective detection limits (except di(2-ethylhexyl)phthalate, which was between 170 and 3300 μg kg⁻¹ dry weight (dw)). Hexabromocyclododecane (HBCD) concentrations were between 0.8 and 6.9 μg kg⁻¹ dw, with highest concentrations at river mouths. Polybrominated diphenylethers (PBDE) concentrations were 0.4–0.6 μg kg⁻¹ dw, decabromodiphenylether (BDE209) 1–32 μg kg⁻¹ dw. The ratio BDE209/PCB153 was used as a tracer for recent emissions, and pointed towards a BDE209 source in the Western Scheldt’s upper estuary. PCBs and PAHs were between 0.19–4.7 and 2.6–200 μg kg⁻¹ dw respectively and generally had highest concentrations at near-shore locations and river mouths.

Responses in the Microtox broad-spectrum and the Mutatox genotoxicity assays were generally low, with near-shore locations giving higher responses. The umu-C genotoxicity and the ER-CALUX assay for estrogenicity showed no response, with the exception of one near-shore location (IJmuiden outer harbour, ER-CALUX).

Highest dioxin-like toxicity (DR-CALUX) was found at near-shore locations, in the outflow of the Rhine/Meuse estuary including a dumping site of harbour sludge. At the Oyster Grounds, DR-CALUX responses appeared to be linked to the occurrence of larger PAHs (4–6 rings). A new, non-destructive clean up procedure resulted in significantly higher DR-CALUX responses than the current protocol. The Dutch legislation on disposal of harbour sludge at sea, dictates the use of the conventional clean up procedure. Our results therefore indicate that probably more dioxin-like toxicity associated with harbour sludge is disposed off at sea than assumed.