The acute toxicity of agricultural surfactants to the tadpoles of four Australian and two exotic frogs

Nonionic surfactants are frequently incorporated into pesticide formulations, and are therefore a group of chemicals to which amphibians may be exposed in agricultural or urban landscapes. However, little is known about the effects of surfactant exposure in amphibians. Feeding stage tadpoles of Bufo marinus, Xenopus laevis and four species of Australian frogs (Crinia insignifera, Heleioporus eyrei, Limnodynastes dorsalis and Litoria moorei) were exposed to nonylphenol ethoxylate (NPE) and alcohol alkoxylate in static-renewal acute toxicity tests. All species exhibited nonspecific narcosis following exposure to both these surfactants. The 48-h EC50 values for NPE ranged between 1.1 mg/l (mild narcosis) and 12.1 mg/l (full narcosis). The 48-h EC50 values for alcohol alkoxylate ranged between 5.3 mg/l (mild narcosis) and 25.4 mg/l (full narcosis). Replicate acute toxicity tests with B. narinus exposed to NPE at 30 degrees C over 96 h indicated that the narcotic effects were not particularly time dependant. The mean 24, 48, 72, and 96-h EC50 (mild narcosis) values were 3.6, 3.7, 3.5 and 3.5 mg/l, respectively. The mean 24, 48, 72 and 96-h EC50 (full narcosis) were 4.0, 4.1, 4.2 and 4.0, respectively. Acute toxicity tests with B. marinus exposed to NPE at 30 degrees C under conditions of low dissolved oxygen (0.8-2.3 mg/l) produced a two to threefold increase in toxicity.     

Formation of PCDDs and PCDFs during the combustion of polyvinylidene chloride

In laboratory-scale combustion of polyvinylidene chloride (PVDC) with a quartz tubular furnace designed and fabricated to provide the desired combustion temperature and mixing state of combustion gas with air, it was found that at 800 degrees C or higher the level of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans [corrected] (PCDDs/PCDFs) resulting from PVDC combustion was no higher than that from heating air alone, and thus far below the levels which resulted from PVDC combustion at 750 degrees C or lower. The results provide the first laboratory confirmation of the relation between PVDC incineration temperature and PCDD/PCDF formation, and of the primary importance of high temperature, turbulence for mixing between air and combustion gas, and sufficient residence time, as governing factors for the minimization of PCDD/PCDF formation in municipal solid waste incinerators.     

A reproducible approach to the reporting of organochlorine compounds in epidemiologic studies

A growing body of research indicates that the most biologically active PCB congeners and organochlorines are not the most abundant components in human and wildlife samples. As researchers attempt measurement on a wider pool of less abundant compounds, they inevitably face quantification problems. To address this problem and enhance comparability across studies, we propose a standardized approach to report organochlorines that is based on a reproducible method to determine the limit of quantification (LQ). Two statistical methods are incorporated into our approach, one by Gibbons termed the Alternative Minimum Level (AML), and one based on determining a region of stable relativestandard deviation in instrument response (RSD). We illustrate our approach using historical samples collected during the 1960s from a cohort of pregnant women enrolled in the Child Health and Development Study. The results are applicable to determining the LQ of any method, and are of utmost importance to environmental scientists conducting trace organic analyses of complex mixtures. Our results demonstrate that: (1) precision as measured by RSD is the most important criterion in determining LQ; (2) the AML routinely isolates a region of constant RSD; and (3) the precision of the instrument detector response as measured with pure standards locates the LQ applicable for real samples - that is, the true limits of quantification reside in the detector, not the matrix effects or analyte recoveries associated with real samples. A corollary of these findings is that bias due to matrix effects and analyte recoveries can be assessed separately from precision and LQdetermination. Previous approaches involved spiking matrix blanks to determine LQ, a problematic strategy for real world, complex matrices. We have now validated the use of pure standards in LQ determination, an approach that is practical and accessible to most analysts.     

The organic precursors affecting the formation of disinfection by-products with chlorine dioxide

The object of this research was to study the formation of disinfection by-products by using chlorine dioxide (ClO2) as a disinfectant reacting with different properties of organic substance in natural aquatic environment. The adsorbent resin (XAD-4, XAD-7) was used to divide the organic matters in raw water into three groups. The influence of the function groups on structure, reaction tendency, and formation of disinfection by-products generated by the reaction of these organic substances with chlorine dioxide was explored. The experimental results show that the three different organic groups formed using adsorbent resin were hydrophobic substance, hydrophilic acid, and non-acid hydrophilics in proportions of 43%, 41%, and 16%, respectively. Within the raw water in our study, the hydrophilic substance had a higher distribution proportion than that described in general articles and journals, which indicates that this water was contaminated with pollution from human beings. The exploration of the reactivity of the three different organic substances with chlorine dioxide shows that the unit consumption of disinfection agent per unit organic matters (represented by ClO2/DOC) is in the following sequence hydrophobic substance > hydrophilic substance > non-acid hydrophilics. It indicated that larger molecular organic precursors had larger consumption of disinfectant. We also discovered that after the reaction of the three different organic substances with chlorine dioxide, the largest amount of disinfection by-products were generated by the non-acid hydrophilics.     

Biodegradation during contaminant transport in porous media: 4. Impact of microbial lag and bacterial cell growth

Miscible-displacement experiments were conducted to examine the impact of microbial lag and bacterial cell growth on the transport of salicylate, a model hydrocarbon compound. The impacts of these processes were examined separately, as well as jointly, to determine their relative effects on biodegradation dynamics. For each experiment, a column was packed with porous medium that was first inoculated with bacteria that contained the NAH plasmid encoding genes for the degradation of naphthalene and salicylate, and then subjected to a step input of salicylate solution. The transport behavior of salicylate was non-steady for all cases examined, and was clearly influenced by a delay (lag) in the onset of biodegradation. This microbial lag, which was consistent with the results of batch experiments, is attributed to the induction and synthesis of the enzymes required for biodegradation of salicylate. The effect of microbial lag on salicylate transport was eliminated by exposing the column to two successive pulses of salicylate, thereby allowing the cells to acclimate to the carbon source during the first pulse. Elimination of microbial lag effects allowed the impact of bacterial growth on salicylate transport to be quantified, which was accomplished by determining a cell mass balance. Conversely, the impact of microbial lag was further investigated by performing a similar double-pulse experiment under no-growth conditions. Significant cell elution was observed and quantified for all conditions/systems. The results of these experiments allowed us to differentiate the effects associated with microbial lag and growth, two coupled processes whose impacts on the biodegradation and transport of contaminants can be difficult to distinguish.     

Development and evaluation of a continuous coarse (PM10-PM2.5) particle monitor

In this paper, we describe the development and laboratory and field evaluation of a continuous coarse (2.5-10 microm) particle mass (PM) monitor that can provide reliable measurements of the coarse mass (CM) concentrations in time intervals as short as 5-10 min. The operating principle of the monitor is based on enriching CM concentrations by a factor of approximately 25 by means of a 2.5-microm cut point round nozzle virtual impactor while maintaining fine mass (FM)--that is, the mass of PM2.5 at ambient concentrations. The aerosol mixture is subsequently drawn through a standard tapered element oscillating microbalance (TEOM), the response of which is dominated by the contributions of the CM, due to concentration enrichment. Findings from the field study ascertain that a TEOM coupled with a PM10 inlet followed by a 2.5-microm cut point round nozzle virtual impactor can be used successfully for continuous CM concentration measurements. The average concentration-enriched CM concentrations measured by the TEOM were 26-27 times higher than those measured by the time-integrated PM10 samplers [the micro-orifice uniform deposit impactor (MOUDI) and the Partisol] and were highly correlated. CM concentrations measured by the concentration-enriched TEOM were independent of the ambient FM-to-CM concentration ratio, due to the decrease in ambient coarse particle mass median diameter with an increasing FM-to-CM concentration ratio. Finally, our results illustrate one of the main problems associated with the use of real impactors to sample particles at relative humidity (RH) values less than 40%. While PM10 concentrations obtained by means of the MOUDI and Partisol were in excellent agreement, CM concentrations measured by the MOUDI were low by 20%, and FM concentrations were high by a factor of 5, together suggesting particle bounce at low RH.     

Genotoxic damage in free-living Algerian mouse (Mus spretus) after the Coto Doñana ecological disaster

The Do?ana National Park (Spain), one of the most important wildlife sites in the West of Europe, was affected (25 April 1998) by the spill of acidic waste rich in toxic metals (mainly zinc, lead, copper, etc.), arsenic and aromatic amines from the Aznalcollar mine accident. Micronuclei test with May Grunwald-Giemsa and with CREST-antikinetocore staining using DAPI as counter-staining were performed on peripheral blood erythrocytes from Algerian mice to evaluate genotoxic damage. Animals were collected in four locations each differently affected by the disaster. Higher frequencies of micronuclei and CREST-positive micronuclei were observed in the sites, which were reached by toxic sludge and contaminated water in comparison with those located within the park. The results obtained applying the two methods indicate that DAPI staining is more sensitive in detecting micronuclei. Genotoxic biomonitoring should be further carried out in the area to control the mutagenetic level in natural populations.     

The Henry's law coefficient of 2-nitrophenol over the temperature range 278-303 K

Although 2-nitrophenol has been identified as an important environmental chemical there is scarcity in the literature regarding the temperature dependence of its Henry's law coefficient, H. Here a bubble purge method was used to measure H for 2-nitrophenol over the temperature range 278-303 K. A novel approach in the data treatment allowed correction of the data for non-equilibrium partitioning in the apparatus to obtain the true equilibrium H value. The experimentally derived temperature-dependent expression for H of 2-nitrophenol is lnH (M atm(-1)) = (6290/T (K)) - 16.6. The standard enthalpy and entropy of gas-to-liquid transfer for 2-nitrophenol in aqueous solution are -52.3 +/- 8.1 kJ mol(-1) and -138 +/- 28 J mol(-1) K(-1), respectively. (Errors are 95% confidence intervals.)     

Metals in sediments and the edible cockle Cerastoderma edule from two Moroccan Atlantic lagoons: Moulay Bou Selham and Sidi Moussa.

Metals (Cd, Cu, Pb and Zn) were determined over a 3-year period in sediments and bivales Cerastoderma edule from two lagoon ecosystems on the Moroccan Atlantic coastline, Moulay Bou Selham and Sidi Moussa. Sediment metal concentrations were seasonally influenced, and were highest, generally, in winter--possibly signifying an increased contribution from run-off from adjacent arable land and roads. Neither site can be considered highly contaminated; however, Cd was enriched at Sidi Moussa, probably as a result of waste discharge from phosphate industries 20 km along the coast to the northeast. This ability to act as a sink for metals at distance from sources demonstrates the need for surveillance in these sensitive environments. Copper and Zn concentrations in edible cockles C. edule appear to be regulated over the concentration ranges currently found in lagoon sediments. In contrast, body burdens of Pb and, to a lesser extent Cd, reflect sediment levels and might be useful in future risk assessments. Metal concentrations Cerastoderma edule are seasonally related to the reproductive cycle, however, and sample timing will need to be standardised in future monitoring exercises.     

Microcosm studies of microbial degradation in a coal tar distillate plume

Investigation of a groundwater plume containing up to 24 g l(-1) phenolic compounds suggested that over a period of nearly 50 years, little degradation had occurred despite the presence of a microbial community and electron acceptors within the core of the plume. In order to study the effect of contaminant concentration on degradation behaviour, laboratory microcosm experiments were performed under aerobic and anaerobic conditions at four different concentrations obtained by diluting contaminated with uncontaminated groundwater. The microcosms contained groundwater with total phenols at ca. 200, 250, 660 and 5000 mg l(-1), and aquifer sediment that had been acclimatised within the plume for several months. The microcosms were operated for a period of 390-400 days along with sterile controls to ascertain whether degradation was microbially mediated or abiotic. Under aerobic conditions, degradation only occurred at concentrations up to 660 mg l(-1) total phenols. At phenol concentrations below 250 mg l(-1) a benzoquinone intermediate, thought to originate from the degradation of 2,5-dimethylphenol, was isolated and identified. This suggested an unusual degradative pathway for this compound; its aerobic degradation more commonly proceeding via catecholic intermediates. Under anaerobic conditions, degradation only occurred in the most dilute microcosm (total phenols 195 mg l(-1)) with a loss of p-cresol accompanied by a nonstoichiometric decrease in nitrate and sulphate. By inference, iron(III) from the sediment may also have been used as a terminal electron acceptor, in which case the amount of biologically available iron released was calculated as 1.07 mg Fe(III)/g of sediment. The study shows that natural attenuation is likely to be stimulated by dilution of the plume.