Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in soil

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (CfP) was studied for 28 days in lab assays using a soil from Germany (A_p horizon, silt loam, and cambisol). Mineralization amounted to 12.40% of applied ¹⁴C after 28 days showing a distinct lag phase until day 7 of incubation. Portions of radioactivity extractable by means of 0.01 M CaCl₂ solution (bioavailable fraction) decreased rapidly and were 4.41% after 28 days. Even immediately after application, only 57.31% were extracted with the aqueous solvent. Subsequent extraction using accelerated solvent extraction (ASE; acetonitrile/water 4:1, v/v) released 39.91% of applied ¹⁴C with day 0 and 26.16% with day 28 of incubation from the samples. Non-extractable portions of radioactivity thus, increased with time amounting to 11.99% (day 0) and 65.00% (day 28). A remarkable increase was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with general microbial activity as determined by DMSO reduction. Analysis of the CaCl₂ and ASE extracts by radio-TLC, radio-HPLC and GC/MS revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed; DT₅₀ values (based on radio-TLC detection of the parent compound) were far below 1 day (CfP) and about 7 days (Cf). TLC analysis pointed to 2-(4-hydroxyphenoxy)-propionic acid as further metabolite. Due to fractionation of non-extractable residues, most of the ¹⁴C was associated with fulvic and humic acids, portions in humin fractions and non-humics were moderate and low, respectively. Using a special strategy, which included pre-incubation of the soil with CfP and then mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the soil examined. The microorganism grew using CfP as sole carbon source with concomitant evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and by 16S rDNA sequence analysis. The sequence exhibited high similarity with that of Rhodococcus wratislaviensis (99.56%; DSM 44107, NCIMB 13082).     

Anticipating Climate Threshold Damages

Several integrated assessment studies have concluded that future learning about the uncertainties involved in climate change has a considerable effect on welfare but only a small effect on optimal short-term emissions. In other words, learning is important but anticipation of learning is not. We confirm this result in the integrated assessment model “model of investment and technological development” for learning about climate sensitivity and climate damages. If learning about an irreversible threshold is included, though, we show that anticipation can become crucial both in terms of necessary adjustments of pre-learning emissions and resulting welfare gains. We specify conditions on the time of learning and the threshold characteristic, for which this is the case. They can be summarized as a narrow “anticipation window.”     

Effects of the pharmaceuticals gemfibrozil and diclofenac on biomarker expression in the zebra mussel (Dreissena polymorpha) and their comparison with standardised toxicity tests

Pharmaceuticals, including the lipid regulator gemfibrozil and the non-steroidal anti-inflammatory drug diclofenac have been identified in waste water treatment plant effluents and receiving waters throughout the western world. The acute and chronic toxicity of these compounds was assessed for three freshwater species (Daphnia magna,Pseudokirchneriella subcapitata, Lemna minor) using standardised toxicity tests with toxicity found in the non-environmentally relevant mid mg L⁻¹ concentration range. For the acute endpoints (IC₅₀ and EC₅₀) gemfibrozil showed higher toxicity ranging from 29 to 59 mg L⁻¹ (diclofenac 47-67 mg L⁻¹), while diclofenac was more toxic for the chronic D. magna 21 d endpoints ranging from 10 to 56 mg L⁻¹ (gemfibrozil 32-100 mg L⁻¹). These results were compared with the expression of several biomarkers in the zebra mussel (Dreissena polymorpha) 24 and 96 h after exposure by injection to concentrations of 21 and 21,000 μg L⁻¹ corresponding to nominal concentrations of 1 and 1000 μg L⁻¹. Exposure to gemfibrozil and diclofenac at both concentrations significantly increased the level of lipid peroxidation, a biomarker of damage. At the elevated nominal concentration of 1000 μg L⁻¹ the biomarkers of defence glutathione transferase and metallothionein were significantly elevated for gemfibrozil and diclofenac respectively, as was DNA damage after 96 h exposure to gemfibrozil. No evidence of endocrine disruption was observed using the alkali-labile phosphate technique. Results from this suite of biomarkers indicate these compounds can cause significant stress at environmentally relevant concentrations acting primarily through oxidation pathways with significant destabilization of the lysosomal membrane and that biomarker expression is a more sensitive endpoint than standardised toxicity tests.     

Complex host marking in the cabbage root fly

Summary. The cabbage root fly marks an oviposition site with two different chemical messages. Plants that were exposed to ovipositing flies are less acceptable than control plants, while sand particles that were closely associated with an actual oviposition site stimulate oviposition. By combining the information from these opposing messages, the cabbage root fly may be able to optimise the size of its egg clusters in relation to the food available for the larvae. The findings might account for the aggregated oviposition observed in this species.     

Development of a Sample Equilibration System for the TEOM Continuous PM Monitor

ABSTRACT

In recent years, scientific discussion has included the influence of thermodynamic conditions (e.g., temperature, relative humidity, and filter face velocity) on PM retention efficiency of filter-based samplers and monitors. Method-associated thermodynamic conditions can, in some instances, dramatically influence the presence of particle-bound water and other light-molecular-weight chemical components such as particulate nitrates and certain organic compounds. The measurement of fine particle mass presents a new challenge for all PM measurement methods, since a relatively greater fraction of the mass is semi-volatile.

The tapered element oscillating microbalance (TEOM) continuous PM monitor is a U.S. Environmental Protection Agency (EPA) PM₁₀ equivalent method (EQPM-1090-079). Several hundred of these monitors are deployed throughout the United States. The TEOM monitor has the unique characteristic of providing direct PM mass measurement without the calibration uncertainty inherent in mass surrogate methods. In addition, it provides high-precision, near-real-time continuous data automatically. Much attention has been given to semi-volatile species retention of the TEOM method.

While using this monitor, it is desirable to maintain as low an operating temperature as practical and to remove unwanted particle-bound water. A new sample equilibration system (SES) has been developed to allow conditioning of the PM sample stream to a lower humidity and temperature level. The SES incorporates a special low-particle-loss Nafion dryer. This paper discusses the configuration and theory of the SES. Performance results include high time-resolved PM_2.5 data comparison between a 30 °C sample stream TEOM monitor with SES and a standard 50 °C TEOM monitor. In addition, 24-hr integrated data are compared with data collected using an EPA PM_2.5 Federal Reference Method (FRM)-type sampler. The SES is a significant development because it can be applied easily to existing TEOM monitors.     

Oviposition of carrot fly (Psila rosae) in response to foliage and leaf surface extracts of host plants

Summary. Foliage of twelve host and two non-host species and surrogate leaves treated with the respective leaf extracts were presented to laboratory populations of the carrot fly (Psila rosae) in oviposition choice assays. The stimulatory activity of dichloromethane surface extracts and the diethyl ether fraction of hot water extracts did not reflect accurately the differences in acceptability observed among intact leaves. A better correlation was found using hexane extracts prepared in a microwave oven. Two out of five fractions of this crude hexane extract obtained by silica gel column chromatography stimulated oviposition. The diethyl ether fraction, which contained the previously identified oviposition stimulants (propenylbenzenes, furanocoumarins, polyacetylenes), could account for only a minor part of the variation in the acceptability of host leaves. The preference hierarchy for intact leaves corresponded better to the ranking of species according to activity of the methanolic fraction, which apparently contains unknown stimulatory compounds.? The water fractions of the hot water extracts were shown to reduce egg-laying underneath surrogate leaves treated with a stimulatory extract. This oviposition-deterring effect was particularly strong with the non-preferred species Pimpinella major, which is also highly resistant in the field. Hence, unidentified inhibitory compounds may also contribute to differential accept ability of host plants. It is concluded that antixenotic (non-preference) resistance of host plants to carrot fly attack depends on complex mixtures of semiochemicals. Received 11 June 1997; accepted 26 November 1997.