New metallothionein assay in Scrobicularia plana: heating effect and correlation with other biomarkers

Metallothionein (MT) and other biomarker levels were measured in Scrobicularia plana clams to assess pollution of the Guadalquivir Estuary possibly affected by metals released from Aznalcóllar pyrite mine in 1998. After optimizing reagent concentrations for monobromobimane derivatization, MT levels were quantified by reversed-phase high-performance liquid chromatography coupled to fluorescence detection (RP-HPLC-FD) in heated or unheated digestive gland extracts and compared to those obtained by differential pulse polarography (DPP). MT content assayed by RP-HPLC-FD in unheated samples was higher than that obtained by DPP and correlated better with metals and anti-oxidant activities. MT assay by RP-HPLC-FD in unheated extracts would be preferable for assessing metal pollution, due to its greater sensitivity and specificity. In addition to MT induction, glyoxalase II inhibition was well correlated with metal contents. Our results suggest that metals at the estuary do not originate from Aznalcóllar spill, but from those carried along by the river and deposited at its concave bank.     

Chemical degradation of 2,3,7,8-TCDD by means of polyethyleneglycols in the presence of weak bases and an oxidant

A chemical method for destroying the 2,3,7,8-TCDD is reported; it provides gradual and progressive substitution of the chlorine atoms by hydrogen atoms. The dehalogenation is promoted by a mixture made up of polyethyleneglycols (high molecular weight) of a weak base (K₂ CO₃) and of an inorganic peroxide (Na₂ O₂) which begins the radical process. The organic chlorine is transformed into inorganic chloride.The reaction mixture administered to male guinea-pigs did not lead to any direct or histological effect.     

CO2 reaction with Ca(OH)2 during SO2 removal with convective pass sorbent injection and high temperature filtration

The Kyoto Protocol calls for greenhouse gas emission reductions which could affect the use of coal for producing electricity. Carbon credits are being explored as a method for countries to meet their reduction commitments. Carbon dioxide removal in flue gas desulfurization (FGD) systems should be considered if and when the concept of carbon credits are implemented. This paper addresses the factors affecting sulfur dioxide removal, including the reaction of carbon dioxide, occurring during convective pass sorbent injection with high temperature filtration for a typical coal-fired power plant. Significant carbonation is found to occur, and the levels are found to depend on injection/filtration temperatures and the residence time on the filter. Ca/S stoichiometry during sorbent injection is found to affect not only the sorbent conversions in the convective pass sorbent injection stage but also the final sorbent conversions in the filtration stage. Even though high sorbent carbonation hinders the sorbent utilization for SO₂ removal, slight alterations in CO₂ concentration are found to have no significant effects on the SO₂ removal of the process.     

Distribution and transport of coal tar-derived PAHs in fine-grained residuum

We investigated the distribution and transport of coal tar-derived polycyclic aromatic hydrocarbons (PAHs) in fine-grained residuum and alluvial floodplain deposits that underlie a former manufactured gas plant. All 16 USEPA priority pollutant PAHs are present at this site and have penetrated the entire 4-5m thickness of clayey sediments, which unconformably overly limestone bedrock. Concentrations of less hydrophobic PAHs (e.g., naphthalene, 0.011-384mg kg(-1)) were about 10 times higher than those of highly hydrophobic PAHs (e.g., benzo[g,h,i]perylene -0.002 to 56.03mgkg(-1)). Microscopic examination of thin-sections of the clay-rich sediments showed that fractures and rootholes, which can act as pathways for flow, occur throughout the profiles. Tarry residue was found coating some fractures and rootholes, indicating that coal tar was, in some cases, able to penetrate as an immiscible phase. However, in the vast majority of samples in which PAHs were detected, there was no detectable tar residue, suggesting that much of the transport occurred in the dissolved phase. Examination of thin-sections with an epifluorescent microscope indicated that PAHs, which fluoresce brightly when exposed to UV light, are distributed throughout the soil matrix, rather than being confined to fractures and rootholes. The widespread distribution of PAHs is most likely due to diffusion-controlled exchange between the fast-flow pathways in the fractures and rootholes and the relatively immobile water in the fine-grained matrix. This implies that fractures and rootholes can play a major role in controlling transport of highly hydrophobic compounds in fine-grained sediments, which would otherwise act as barriers to contaminant migration.     

Development of an analytical method for analysis of flubendiamide,des-iodo flubendiamide and study of their residue persistence in tomato and soil

Flubendiamide is a new insecticide that has been found to give excellent control of lepidopterous pests of tomato. This study has been undertaken to develop an improved method for analysis of flubendiamide and its metabolite des-iodo flubendiamide and determine residue retention in tomato and soil. The analytical method developed involved extraction of flubendiamide and its metabolite des-iodo flubendiamide with acetonitrile, liquid-liquid partitioning into hexane-ethyl acetate mixture (6:4, v v^?1) and cleanup with activated neutral alumina. Finally the residues were dissolved in gradient high pressure liquid chromatography (HPLC) grade acetonitrile for analysis by HPLC. The mobile phase, acetonitrile-water at 60:40 (v v^?1) proportion and the wavelength of 235 nm gave maximum peak resolution. Using the above method and HPLC parameters described, nearly 100 % recovery of both insecticides were obtained. There was no matrix interference and the limit of quantification (LOQ) of the method was 0.01 mg kg^?1. Initial residue deposits of flubendiamide on field-treated tomato from treatments @ 48 and 96 g active ingredient hectare^?1 were 0.83 and 1.68 mg kg^?1,respectively. The residues of flubendiamide dissipated at the half-life of 3.9 and 4.4 days from treatments @ 48 and 96 g a.i. ha^?1, respectively and persisted for 15 days from both the treatments. Des-iodo flubendiamide was not detected in tomato fruits at any time during the study period. Residues of flubendiamide and des-iodo flubendiamide in soil from treatment @ 48 and 96 g a.i. ha^?1 were below detectable level (BDL, < 0.01 mg kg^?1) after 20 days. Flubendiamide completely dissipated from tomato within 20 days when the 480 SC formulation was applied at doses recommended for protection against lepidopterous pests.     

Determination of organochlorine and organophosphate pesticide residues in fruits,vegetables and sediments

Abstract

A method is described for the determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments. The concentrated solvent extract was sealed in a polymeric membrane tube, dialysed in cyclohexane and the solvent replaced with hexane. The organophosphates were analysed on a specific thermionic detector without further clean‐up. For the organochlorine pesticides the extract was eluted through 3 g of alumina and analysed on GC/ECD. The clean‐up for sediment extract was carried out on a10 g alumina column with 100 mL hexane containing 5% acetone and the eluate was concentrated to 5 mL.

The detection limit for organophosphates on a 40 g sample and a final volume of 10 mL was on the average 0.01 mg/kg. The detection limit for organochlorine pesticides, with the final volume of 25 mL, was 0.005 mg/kg for all pesticides except for p,p'‐DDT and endosulfan sulphate, which was 0.01 mg/kg.

The detection limit for oganochlorine pesticides in sediment, with the final volume of 2 mL, was less than 1 μg/kg and for organophosphate pesticides less than 10 μg/kg when the final volume was made to 0.5 mL. At the detection limits the method produced a very high coefficient of variation for both organochlorine and organophosphate pesticides.     

Deriving environmental quality standards in European surface waters: when are there too few data?

Recent technical guidance has been published by the European Commission that outlines methodologies for the derivation of Environmental Quality Standards (EQS) in European surface waters under the Water Framework Directive (WFD). The guidance allows the derivation of a long-term EQS from a small dataset. Specifically an EQS can be derived from just three acute data points, although the safety factors built into such an EQS are large (e.g. up to a factor of 1,000). Large safety factors make such EQS uncertain, and often difficult to achieve in practice. We examine dataset requirements for the derivation of EQS and specifically the minimum number of tests needed for setting EQS for long-term chemical exposures that result in reduced relative uncertainty, as assessed simply through the reduction in standard deviation of the means of the values derived. Using ecotoxicity datasets for four example chemicals, for which EQS have been derived in many jurisdictions, we show that variation in the EQS is greatest when using the minimum dataset allowable under the WFD guidance, but decreases rapidly when seven or more datapoints are available. Increasing the minimum number of ecotoxicity data in deriving an EQS results in a greater understanding of ecotoxicological effects. With this knowledge, the mitigating effects of water chemistry can be accounted for in deriving an EQS, even with relatively limited datasets. The new guidance suggests “simplistic” approaches to account for chemical availability, but does not detail how this might be undertaken. We provide examples of ways by which water chemistry effects can be included in deriving implementable EQS for metals with relatively few reliable and relevant data.     

Carbon accumulation through ecosystem recovery

A market has emerged for carbon sequestered through reforestation. The opportunity to restore ecosystems through this market rather than establish plantations is demonstrated by an Australian case study. In the state of Queensland there are vast areas that have been cleared relatively recently and could be restored to ecosystems with high resilience and important biodiversity values with appropriate management. In order to foster opportunities for carbon accumulation through ecosystem recovery spatially explicit information on sequestration rates, management recommendations, and clear definitions of ancillary biodiversity benefits need to be defined.