Acute toxicity tests with Daphnia magna, Americamysis bahia, Chironomus riparius and Gammarus pulex and implications of new EU requirements for the aquatic effect assessment of insecticides

Threshold concentrations for treatment related effects of 31 insecticides, as derived from aquatic micro-/mesocosm tests, were used to calibrate the predictive value of the European Tier-1 acute effect assessment on basis of laboratory toxicity tests with Daphnia magna, Chironomus spp., Americamysis bahia and Gammarus pulex. The acute Tier-1 effect assessment on basis of Daphnia (EC(50)/100) overall was protective for organophosphates, carbamates and most pyrethroids but not for neonicotinoids and the majority of insect growth regulators (IGRs) in the database. By including the 28-day water-spiked Chironomus riparius test, the effect assessment improves but selecting the lowest value on basis of the 48-h Daphnia test (EC50/100) and the 28-day Chironomus test (NOEC/10) is not fully protective for 4 out of 23 insecticide cases. An assessment on basis of G. pulex (EC(50)/100) is sufficiently protective for 15 out of 19 insecticide cases. The Tier-1 procedure on basis of acute toxicity data (EC(50)/100) for the combination of Daphnia and A. bahia and/or Chironomus (new EU dossier requirements currently under discussion) overall is protective to pulsed insecticide exposures in micro-/mesocosms. For IGRs that affect moulting, the effect assessment on basis of the 48-h Chironomus test (EC(50)/100) may not always be protective enough to replace that of the water-spiked 28-day C. riparius test (NOEC/10) because of latency of effects.     

Adapting a geographical information system-based water resource management to the needs of the Romanian water authorities

Background, aim, and scope

The need for global and integrated approaches to water resources management, both from the quantitative and the qualitative point of view, has long been recognized. Water quality management is a major issue for sustainable development and a mandatory task with respect to the implementation of the European Water Framework Directive as well as the Swiss legislation. However, data modelling to develop relational databases and subsequent geographic information system (GIS)-based water management instruments are a rather recent and not that widespread trend. The publication of overall guidelines for data modelling along with the EU Water Framework Directive is an important milestone in this area. Improving overall water quality requires better and more easily accessible data, but also the possibility to link data to simulation models. Models are to be used to derive indicators that will in turn support decision-making processes. For this whole chain to become effective at a river basin scale, all its components have to become part of the current daily practice of the local water administration. Any system, tool, or instrument that is not designed to meet, first of all, the fundamental needs of its primary end-users has almost no chance to be successful in the longer term.

Materials and methods

Although based on a pre-existing water resources management system developed in Switzerland, the methodological approach applied to develop a GIS-based water quality management system adapted to the Romanian context followed a set of well-defined steps: the first and very important step is the assessment of needs (on the basis of a careful analysis of the various activities and missions of the water administration and other relevant stakeholders in water management related issues). On that basis, a conceptual data model (CDM) can be developed, to be later on turned into a physical database. Finally, the specifically requested additional functionalities (i.e. functionalities not provided by classical commercial GIS software), also identified during the assessment of needs, are developed. This methodology was applied, on an experimental basin, in the Ialomita River basin.

Results

The results obtained from this action-research project consist of a set of tangible elements, among which (1) a conceptual data model adapted to the Romanian specificities regarding water resources management (needs, data availability, etc.), (2) a related spatial relational database (objects and attributes in tables, links, etc.), that can be used to store the data collected, among others, by the water administration, and later on exploited with geographical information systems, (3) a toolbar (in the ESRI environment) offering the requested data processing and visualizing functionalities. Lessons learned from this whole process can be considered as additional, although less tangible, results.

Discussion

The applied methodology is fairly classical and did not come up with revolutionary results. Actually, the interesting aspects of this work are, on the one hand, and obviously, the fact that it produced tools matching the needs of the local (if not national) water administration (i.e. with a good chance of being effectively used in the day-to-day practice), and, on the other hand, the adaptations and adjustments that were needed both at the staff level and in technical terms.

Conclusions

This research showed that a GIS-based water management system needs to be backed by some basic data management tools that form the necessary support upon which a GIS can be deployed. The main lesson gained is that technology transfer has to pay much attention to the differences in existing situations and backgrounds in general, and therefore must be able to show much flexibility. The fact that the original objectives could be adapted to meet the real needs of the local end-users is considered as a major aspect in achieving a successful adaptation and development of water resources management tools. Time needed to setup things in real life was probably the most underestimated aspect in this technology transfer process.

Recommendations and perspectives

The whole material produced (conceptual data model, database and GIS tools) was disseminated among all river basin authorities in Romania on the behalf of the national water administration (ANAR). The fact that further developments, for example, to address water quantity issues more precisely, as envisaged by ANAR, can be seen as an indication that this project succeeded in providing an appropriate input to improve water quality in Romania on the long term.

     

Influence of natural events on the concentration and composition of atmospheric particulate matter

A ten-month field study aimed to determine the contribution of natural events (i.e. sea-salt and mineral dust events) to urban PM concentration was carried out at six sampling sites in Central Italy (Lazio region). Four indicators have been used to identify natural events during the period of the study. The first one is constituted by the ratio between number of particles in the coarse to the accumulation mode. It is simple, cheap, and the information are given in quasi-real time, but the nature of the event (sea-salt or mineral dust) is not detectable. The second indicator relies on the chemical analysis of the collected PM by X-ray fluorescence (XRF) and allows a robust identification of sea-salt and crustal components. The third one is based on diagnostic ratios of elemental fractions: Mg_extractable/Ti_residue for sea-salt and Ti_residue/Sb_residue for mineral dust. It requires skilled staff but it is most accurate and sensible. The last indicator, constructed on the basis of natural radioactivity data, is not diagnostic for the nature of the event but it is able to estimate the increase in PM concentration with respect to the expected concentration in the absence of natural events.The relevance of natural events and the variations in PM concentration and composition during the study are discussed. The joined use of the four indicators allowed the identification of about 20 natural PM episodes. In general, sea-salt aerosol events did not cause exceedance of the daily EU limit value for PM₁₀. Saharan dust events, instead, were in most cases responsible for the exceedance of the limit value at all stations.     

Evaluation of relative photonic efficiency in heterogeneous photocatalytic reactors

The evaluation of photonic efficiency in heterogeneous photocatalysis remains elusive because the number of absorbed photons is difficult to assess experimentally. The photonic efficiency of heterogeneous photocatalytic reactors depends on the reactor geometry, irradiation source, and photocatalyst properties. In this work, the relative photonic efficiency of heterogeneous photocatalytic reactors to degrade an azo dye was evaluated using phenol as the standard system. The experimental tests were carried out in a batch reactor under different conditions of pH, catalyst dosage, initial concentration, and ultraviolet (UV) lamps. The kinetics of disappearance of both phenol and azo dye were studied using the initial rate method and were described according to the Langmuir-Hinshelwood (L-H) kinetic model. It was observed that the relative photonic efficiency depends on the adsorption/desorption properties of the photocatalyst.     

Solvent and surfactant enhanced solubilization, stabilization, and degradation of amitraz

In an effort to help with the development of effective dip vat management and waste disposal strategies this study determined how solution properties such as pH, buffer composition, ionic strength, temperature, solubility in organic solvents and the addition of commonly used solubilizing agents influenced the hydrolysis of amitraz. Amitraz degrade by means of hydrolysis described by a pseudo-first order rate process and a type ABCD pH rate profile. Hydrolysis increased with temperature and was fastest at low pH, slowest at neutral to slightly alkaline pH, and slightly increased above pH 10. However, buffer concentration and ionic strength influenced the hydrolysis rate and had to be accounted for before constructing a pH rate profile. Hydrolysis seems to depend on the dielectric constant of solvent mixtures and was fastest in water, slower in propylene glycol and ethanol solutions, and slowest in DMSO mixtures. In surfactant solutions, anionic micelles enhanced and cationic micelles retarded the hydrolysis rate. The magnitude of micellar effects decreased with increasing concentrations of the surfactants. The increased solubility and faster hydrolysis of amitraz in the sodium lauryl sulfate solutions showed that anionic surfactants potentially could be used for cleaning up amitraz spills, because it both solubilized the drug and catalyzed hydrolysis.     

Comparing aquatic risk assessment methods for the photosynthesis-inhibiting herbicides metribuzin and metamitron

Three different risk assessment procedures are described that aim to protect freshwater habitats from risks of the photosynthesis-inhibiting herbicides metribuzin and metamitron. These procedures are (1) the first-tier approach, based on standard toxicity tests and the application of an assessment factor, (2) the Species Sensitivity Distribution (SSD) approach, based on laboratory tests with a wider array of species and the application of a statistical model to calculate the HCx (the Hazardous Concentration for x% of the species), and (3) the model ecosystem approach, based on the evaluation of treatment-related effects in field enclosures. A comparison of the risk assessment procedures reveals that the first-tier approach is the most conservative for metamitron and metribuzin, and that HC5 values (and even HC10 values) based on acute EC50 values of algae and aquatic vascular plants may be used to derive maximum permissible concentrations for single applications. For both compounds these HC5 values were very similar to the ecological threshold concentrations in the enclosure studies. In contrast to model ecosystem experiments, however, HCx values based on lab toxicity tests do not provide information on the recovery potential of sensitive endpoints and on indirect effects, which may be important for regulatory decision-making. In the enclosure study, indirect effects of metribuzin on invertebrate populations were observed at an exposure concentration that was approximately 20 times lower than the corresponding HC5 value based on lab toxicity data for aquatic invertebrates.     

Chlorination of bisphenol A: kinetics and by-products formation

The kinetics of initial chlorination of bisphenol A (BPA) was studied between pH 2 and 11 at room temperature (20 +/- 2 degrees C). pH Profile of the apparent second-order rate constant of the reaction of BPA with chlorine were modeled considering the elementary reactions of HOCl with BPA species and an acid-catalyzed reaction. The predominant reactions at near neutral pH were the reactions of HOCl with the two phenolate species of BPA (k = 3.10 x 10(4) M(-1)s(-1) for BPA- and 6.62 x 10(4) M(-1) s(-1) for BPA(2-)). At near neutral pH, half-life times of BPA were calculated to be less than 1.5 h for chlorine residual higher than 0.2 mg l(-1). Chlorination of synthetic treated waters spiked with BPA showed that BPA disappeared within 4 h and that chlorinated bisphenol A congeners were rapidly formed and remained in solution for up to 10-20 h when low chlorine dosages are applied (0.5-1 mg l(-1)). To limit their presence in drinking water networks, it is then necessary to maintain high chlorine residuals that rapidly produce and decompose chlorinated bisphenol A congeners.     

Temperature dependence of Henry's law constants of metolachlor and diazinon

A dynamic system based on the water/air equilibrium at the interface within the length of a microporous tube has been used to determine experimentally the Henry's law constants (HLC) of two pesticides: metolachlor and diazinon. The measurements were conducted over the temperature range 283-301 K. At 293 K, HLCs values are (42.6+/-2.8) x 10(3) (in units of M atm(-1)) for metolachlor and (3.0+/-0.3)x10(3) for diazinon. The obtained data were used to derive the following Arrhenius expressions: HLC=(3.0+/-0.4) x 10(-11) exp((10,200+/-1,000)/T) for metolachlor and (7.2+/-0.5) x 10(-15) exp((11,900+/-700)/T) for diazinon. At a cumulus cloud temperature of 283 K, the fractions of metolachlor and diazinon in the atmospheric aqueous phase are about 57% and 11% respectively. In order to evaluate the impact of a cloud on the atmospheric chemistry of both studied pesticides, we compare also their atmospheric lifetimes under clear sky (tau(gas)), and cloudy conditions (tau(multiphase)). The calculated multiphase lifetimes (in units of hours) are significantly lower than those in gas phase at a cumulus temperature of 283 K (in parentheses): metolachlor, 0.4 (2.9); diazinon, 1.9 (5.0).     

Enhanced solubilization of arsenic and 2,3,4,6 tetrachlorophenol from soils by a cyclodextrin derivative

The application of extracting aqueous solutions with cyclodextrins in several soil remediation technologies has been increasingly studied but little is known about their removal capacities toward the inorganic species. Herein, the effectiveness of cyclodextrins (CDs) in extracting arsenic, copper, and iron from a mining soil is presented. In a preliminary test of four types of CD aqueous solutions, only the addition of carboxylmethyl-beta-cyclodextrin CMCD (a cyclodextrin derivative) led to a significant enhancement in arsenic removal. An increase in the concentration of copper and iron in the leachates was also observed with CMCD. Kinetic study of arsenic release was carried out at two temperatures (20 and 35 degrees C). The arsenic concentration in the leachates increases with increasing cyclodextrin concentration. At an 80 mM CMCD concentration, arsenic, copper, and iron released in filtrates were about 20-, 1,000-, and 4,000-fold greater, respectively, than that obtained using deionized water. In the soil system, the CMCD capacity removal was found to be higher for cations than for arsenic. Because the tetrachlorophenol can co-occur with arsenic and copper in several contaminated sites, its solubilization by CMCD was also investigated. Extraction experiments were performed to extract 2,3,4,6 tetrachlorophenol (TeCP) in spiked soil with CMCD. The results of batch experiments have shown that CMCD could significantly increase the TeCP extraction from soil. CD sorption on soils as quantified by a fluorescence technique was low, indicating no significant loss of CD during the leaching experiments. The use of CMCD as a flushing agent to enhance the removal of both inorganic and organic pollutants from mixed-contaminated soils appears as a promising remediation method.     

Irrigation runoff insecticide pollution of rivers in the Imperial Valley, California (USA)

The Alamo and New Rivers located in the Imperial Valley, California receive large volumes of irrigation runoff and discharge into the ecologically sensitive Salton Sea. Between 1993 and 2002 we conducted a series of studies to assess water quality using three aquatic species: a cladoceran (Ceriodaphnia dubia), a mysid (Neomysis mercedis), and a larval fish (Pimephales promelas). Although no mortality was observed with the P. promelas, high-level toxicity to the invertebrate species was documented in samples from both rivers during many months of each year. Toxicity identifications and chemical analyses identified the organophosphorus insecticides (OP), chlorpyrifos and diazinon, as the cause of C. dubia toxicity. The extent of the C. dubia mortality was highly correlated with quantities of these OPs applied in the river watersheds. C. dubia mortality occurred during more months of our 2001/2002 study than in the 1990s investigations. During 2001/2002, the extensive C. dubia mortality observed in New River samples was caused by OP insecticide pollution that originated from Mexico. Mortality to N. mercedis in New River samples was likely caused by contaminants other than OP insecticides. Our studies document OP insecticide-caused pollution of the Alamo River over a 10-year period and provide the necessary information for remediation efforts.