A pesticide emission model (PEM) Part I: model development

The application of pesticides to cultivated soil and crops is a major source of pesticides that are found in the atmosphere and which are transported and deposited to land and water surfaces over distances that range from local to global scales. In this first part of a two-part paper, a pesticide emission model (PEM) is proposed for estimating the exchange with the atmosphere of pesticides applied to soils and crops. The basis of PEM is a one-dimensional numerical solution of the dynamic equations describing the advection and diffusion of heat, moisture and pesticide within the soil column and exchange with the atmosphere through heat transfer, evapotranspiration and volatilization. The soil model is coupled with an atmospheric surface layer and a simple canopy model that includes: the interception of sprayed pesticide by the crop foliage; the partitioning of pesticide within a wet or dry canopy; and, the volatilization of pesticide to the atmosphere or the wash-off to the soil by precipitation. The finite-element technique used for solving the model equations is mass conservative and multi-year periods of simulation are possible while maintaining a proper mass balance of pesticide in the soil. The model is solved using 1200 s time-steps and 49 variably spaced levels in the soil to a depth of 2 m, with the highest vertical resolution (0.002 m spacing) near the soil surface. Similarity theory is used to parameterize the fluxes of heat, moisture and pesticide through the atmospheric surface layer with hourly meteorology being provided by either climate station observations or a meteorological model. In the second part to this paper, the results of an evaluation of PEM are reported.     

Modelling pesticide volatilization after soil application using the mechanistic model Volt'Air

Volatilization of pesticides participates in atmospheric contamination and affects environmental ecosystems including human welfare. Modelling at relevant time and spatial scales is needed to better understand the complex processes involved in pesticide volatilization. Volt'Air-Pesticides has been developed following a two-step procedure to study pesticide volatilization at the field scale and at a quarter time step. Firstly, Volt'Air-NH₃ was adapted by extending the initial transfer of solutes to pesticides and by adding specific calculations for physico-chemical equilibriums as well as for the degradation of pesticides in soil. Secondly, the model was evaluated in terms of 3 pesticides applied on bare soil (atrazine, alachlor, and trifluralin) which display a wide range of volatilization rates. A sensitivity analysis confirmed the relevance of tuning to K_h. Then, using Volt'Air-Pesticides, environmental conditions and emission fluxes of the pesticides were compared to fluxes measured under 2 environmental conditions. The model fairly well described water temporal dynamics, soil surface temperature, and energy budget. Overall, Volt'Air-Pesticides estimates of the order of magnitude of the volatilization flux of all three compounds were in good agreement with the field measurements. The model also satisfactorily simulated the decrease in the volatilization rate of the three pesticides during night-time as well as the decrease in the soil surface residue of trifluralin before and after incorporation. However, the timing of the maximum flux rate during the day was not correctly described, thought to be linked to an increased adsorption under dry soil conditions. Thanks to Volt'Air's capacity to deal with pedo-climatic conditions, several existing parameterizations describing adsorption as a function of soil water content could be tested. However, this point requires further investigation. Practically speaking, Volt'Air-Pesticides can be a useful tool to make decision about agricultural practices such as incorporation or for the estimation of overall pesticide volatilization rates, and it holds promise for time specific dynamics.     

Measurement of trifluralin volatilization in the field: Relation to soil residue and effect of soil incorporation

Volatilization may represent a major dissipation pathway for pesticides applied to soils or crops. A field experiment (September, 2002), consisted in volatilization fluxes measurements during 6 days, covering the periods before and after soil incorporation carried out 24 h after trifluralin spraying on bare soil. Evolution of concentration in soil was measured during 101 days, together with soil physical and meteorological variables. Volatilization fluxes were very high immediately after application (1900 ng m(-2) s(-1)), decreased down to 100 ng m(-2) s(-1) in the following 24 h. Soil incorporation strongly abated trifluralin concentration in the air. 99% of the total volatilization losses recorded over the 6 days following application occurred before incorporation. Volatilization fluxes evidenced a diurnal cycle driven by environmental conditions. Soil trifluralin residues could still be quantified 101 days after application. Our results highlight the caution required when using soil degradation half-life values in the field for volatile compounds.     

Prediction of pesticide volatilization with PELMO 3.31

In the current EU risk assessment for pesticide registration, the European Community requires prediction of the concentration of each pesticide in air. A number of mathematical models are used to assess the fate of pesticides in groundwater, surface water and soil. PELMO 3.20 calculates the volatilization fluxes from bare soil and was improved in the new version PELMO 3.31 to include the effect of temperature and sorption in dry soil. The objective of this study was to evaluate the new version of PELMO 3.31 in predicting the pesticide volatilization under field conditions. Procymidone, malathion, and ethoprophos were the test compounds in two different seasons (autumn and winter). Comparing simulation results obtained with PELMO 3.31, after calibration, with the previous version PELMO 3.20 shows that the estimated volatilization results seems improved for malathion, similar or slightly overestimating in the warmer season for ethoprophos, and similar or slightly underestimating in the colder season for procymidone. The new release of PELMO allows a more accurate estimation of pesticides volatilization from soil as function of meteorological factors, especially for medium or low volatility pesticides. Some difficulties remain, such as the determination of the active air layer and the sorption increment with the soil drying.     

Dynamic flux chamber measurement of gaseous mercury emission fluxes over soils: Part 2—effect of flushing flow rate and verification of a two-resistance exchange interface simulation model

Both field and laboratory tests demonstrated that soil Hg emission fluxes measured by dynamic flux chamber (DFC) operations strongly depend on the flushing air flow rates used. The general trend is an increase in the fluxes with increasing flushing flow rates followed by an asymptotic approach to flux maximum at sufficiently high (optimum) flushing flow rates. This study indicates that the DFC measurements performed at low flushing flow rates can underestimate Hg emission fluxes over soils, especially Hg-enriched soils. High flushing flow rates therefore are recommended for accurate estimation of soil Hg emission fluxes by DFC operations. The dependence of DFC-measured soil Hg emission fluxes on flushing flow rate is a physical phenomenon inherent in DFC operations, regardless of DFC design and soil physical characteristics. Laboratory tests using DFCs over different soils confirmed the predictions of a two-resistance exchange interface model and demonstrated the capability of this model in quantitatively simulating Hg emissions from soils measured by DFC operations.     

Dynamic flux chamber measurement of gaseous mercury emission fluxes over soils. Part 1: simulation of gaseous mercury emissions from soils using a two-resistance exchange interface model

A two-resistance exchange interface model (TREIM) was developed to simulate gaseous mercury (Hg) emissions from soils measured by dynamic flux chamber (DFC) operations. The model is based on mass balance principles and a Hg air/soil exchange theory that considers the influence of flushing flow rate on Hg air/soil exchange. We used this model to examine the effect of the flushing flow rate and understand the optimum conditions for DFC measurements of Hg emission fluxes over soils. Our model simulations indicate that the flushing flow rate is a most critical operation condition. We recommend adoption of high flushing flow rates (e.g., ∼15–40 l min⁻¹ for DFCs of common design) based on our simulation findings that underestimation of actual emission fluxes can occur at low flushing flow rates. The biased low fluxes are caused by suppression of emission potential resulting from internal accumulation of emitted Hg and by higher exchange resistance both at low flushing flow rates. This model provides a useful means for estimating maximum steady-state fluxes and soil air Hg concentrations and for adjustment of the fluxes measured under different operating conditions. The model also finds its value in understanding mechanical processes of Hg emissions from soils.     

Reduction of the movement and persistence of pesticides in soil through common agronomic practices

Laboratory and field studies were conducted in order to determine the leaching potential of eight pesticides commonly used during pepper cultivation by use of disturbed soil columns and field lysimeters, respectively. Two soils with different organic matter content (soils A and B) were used. Additionally, soil B was amended with compost (sheep manure). The tested compounds were cypermethrin, chlorpyrifos-methyl, bifenthrin, chlorpyrifos, cyfluthrin, endosulfan, malathion and tolclofos-methyl. In soil B (lower organic matter content), only endosulfan sulphate, malathion and tolclofos-methyl were found in leachates. For the soil A (higher organic matter content) and amended soil B, pesticide residues were not found in the leachates. In addition, this paper reports on the use of common agronomic practices (solarization and biosolarization) to enhance degradation of these pesticides from polluted soil A. The results showed that both solarization and biosolarization enhanced the degradation rates of endosulfan, bifenthrin and tolclofos-methyl compared with the control. Most of the studied pesticides showed similar behavior under solarization and biosolarization conditions. However, chlorpyrifos was degraded to a greater extent in the solarization than in biosolarization treatment. The results obtained point to the interest in the use of organic amendment in reducing the pollution of groundwater by pesticide drainage and in the use of solarization and biosolarization in reducing the persistence of pesticides in soil.     

Bound residues of organic compounds in the soil: the significance of pesticide persistence in soil and water: a European regulatory view

The paper discusses key aspects of the European Union (EU) regulatory policy for persistence of agricultural pesticide active substances (a.s.) in soil, which is examined in the context of the EU Authorisations Directive (91/414/EEC). For agricultural pesticide regulation within EU Member States (MS), the Authorisations Directive will gradually replace existing national systems. Discussion is concentrated on this directive, looking in particular at the Uniform Principles therein and the possible ways that these decision-making guidelines could be developed into a regulatory framework. The aim in this process of negotiated development is to identify any questions or data requirements that will be needed for persistent pesticides, over and above those generally required for all compounds. The present European regulatory position on soil non-extractable or bound residues is discussed. Finally, a brief mention of pesticide persistence in water and sediment is made.     

Sorption kinetics of 2,4-D and carbaryl in selected agricultural soils of northern Iraq: application of a dual-rate model

Agriculture in northern Iraq (Kurdistan) relies on the widespread use of pesticides to promote crop performance. Over-application of many pesticides is commonplace, however, and may compromise soil and water quality, and ultimately human health, within the region. The aim of this study was to investigate the sorption-desorption kinetics and equilibrium partitioning of two selected pesticides in agricultural soils from northern Iraq. This was achieved by fitting a dual-rate sorption-desorption model to time-dependent data obtained from batch experiments. 2,4-D and carbaryl were selected for scrutiny since both are in common use in the region. Six agricultural soils, sampled around the city of Erbil, were investigated. These were low in organic carbon (OC) compared with many agricultural soils from more temperate regions. However, there was still a clear trend of increasing sorption of both 2,4-D and carbaryl with increasing % OC. In the case of both compounds, fast and slow adsorption rate coefficients and 48 h experimental K(d) values were positively correlated with % OC. It was assumed that K(OC) would provide a simple and reliable predictor of K(d). However, while this assumption holds true for short-term (48 h) experimental data, longer-term sorption in some soils (as indicated by theoretical K(d) values estimated from kinetic parameters in our study) appears to be under-predicted by K(OC) alone. The data presented here provide a useful starting point for further site-specific investigations of pesticide impacts in the Kurdistan region of Iraq.     

Model approach for estimating potato pesticide bioconcentration factor

We presented a model that estimates the bioconcentration factor (BCF) of pesticides in potatoes supposing that the pesticide in the soil solution is absorbed by the potato by passive diffusion, following Fick's second law. The pesticides in the model are nonionic organic substances, traditionally used in potato crops that degrade in the soil according to a first-order kinetic equation. This presents an expression that relates BCF with the pesticide elimination rate by the potato, with the pesticide accumulation rate within the potato, with the rate of growth of the potato and with the pesticide degradation rate in the soil. BCF was estimated supposing steady state equilibrium of the quotient between the pesticide concentration in the potato and the pesticide concentration in the soil solution. It is suggested that a negative correlation exists between the pesticide BCF and the soil sorption partition coefficient. The model was built based on the work of Trapp et al. [Trapp, S., Cammarano, A., Capri, E., Reichenberg, F., Mayer, P., 2007. Diffusion of PAH in potato and carrot slices and application for a potato model. Environ. Sci. Technol. 41 (9), 3103-3108], in which an expression to calculate the diffusivity of persistent organic substances in potatoes is presented. The model consists in adding to the expression of Trapp et al. [Trapp, S., Cammarano, A., Capri, E., Reichenberg, F., Mayer, P., 2007. Diffusion of PAH in potato and carrot slices and application for a potato model. Environ. Sci. Technol. 41 (9), 3103-3108] the hypothesis that the pesticide degrades in the soil. The value of BCF suggests which pesticides should be monitored in potatoes.     

Assessing pesticide concentrations and fluxes in the stream of a small vineyard catchment - Effect of sampling frequency

This study reports on the occurrence and behaviour of six pesticides and one metabolite in a small stream draining a vineyard catchment. Base flow and flood events were monitored in order to assess the variability of pesticide concentrations according to the season and to evaluate the role of sampling frequency on the evaluation of fluxes estimates. Results showed that dissolved pesticide concentrations displayed a strong temporal and spatial variability. A large mobilisation of pesticides was observed during floods, with total dissolved pesticide fluxes per event ranging from 5.7 × 10⁻³ g/Ha to 0.34 g/Ha. These results highlight the major role of floods in the transport of pesticides in this small stream which contributed to more than 89% of the total load of diuron during August 2007. The evaluation of pesticide loads using different sampling strategies and method calculation, showed that grab sampling largely underestimated pesticide concentrations and fluxes transiting through the stream.     

Key parameters and practices controlling pesticide degradation efficiency of biobed substrates

We studied the contribution of each of the components of a compost-based biomixture (BX), commonly used in Europe, on pesticide degradation. The impact of other key parameters including pesticide dose, temperature and repeated applications on the degradation of eight pesticides, applied as a mixture, in a BX and a peat-based biomixture (OBX) was compared and contrasted to their degradation in soil. Incubation studies showed that straw was essential in maintaining a high pesticide degradation capacity of the biomixture, whereas compost, when mixed with soil, retarded pesticide degradation. The highest rates of degradation were shown in the biomixture composed of soil/compost/straw suggesting that all three components are essential for maximum biobed performance. Increasing doses prolonged the persistence of most pesticides with biomixtures showing a higher tolerance to high pesticide dose levels compared to soil. Increasing the incubation temperature from 15 °C to 25 °C resulted in lower t(1/2) values, with biomixtures performing better than soil at the lower temperature. Repeated applications led to a decrease in the degradation rates of most pesticides in all the substrates, with the exception of iprodione and metalaxyl. Overall, our results stress the ability of biomixtures to perform better than soil under unfavorable conditions and extreme pesticide dose levels.     

Survey of organochlorine pesticides in horticultural soils and there grown Cucurbitaceae

Organochlorine pesticides (OCP) are still found in food and feed crops although they were applied about 40 years ago. There is a considerable knowledge gap concerning the extent of soil and crop contamination by OCP. We performed two surveys in 2002 and 2005 to assess the loads of OCP in 41 Swiss horticultural fields under organic and conventional production and corresponding Cucurbitaceae fruits (cucumbers, zucchini, and pumpkin), whereas these fields stay for intensive agricultural production in Europe. In addition, soil organic carbon, texture, and pH were measured also. OCP were detected in 27 out of 41 fields (65.9%). The farming practice had no influence on the contamination or level of OCP in soil. The sum of OCP-loads per field ranged from <0.01 to 1.3mgkg(-1) dry soil and pentachloroaniline (PCA, 2.1mgkg(-1)), p,p'-DDT (0.5mgkg(-1)), and p,p'-DDE and dieldrin (0.4mgkg(-1)) were the most detected pesticides over all investigated soils. PCA (up to 0.02mgkg(-1)), dieldrin (up to 0.04mgkg(-1)), alpha-chlordane and cis-heptachloroepoxide (<0.01mgkg(-1)) were detected in five cucumber samples out of 41 Cucurbitaceae samples. Statistical analysis revealed no significant influence of the measured soil properties on the OCP-load of soils and cucumbers, although there is evidence that the bioavailability of OCP in soils to Cucurbitaceae plants was influenced by the sorption of the compounds to soil organic matter and by the polarity of the pesticide molecules. It is suggested, that OCP contamination is widespread in all European regions with intensive plant production and associated pesticide use, and deserves more attention with respect to save food production.     

Absorption of current use pesticides by snapping turtle (Chelydra serpentina) eggs in treated soil

Reptiles often breed within agricultural and urban environments that receive frequent pesticide use. Consequently, their eggs and thus developing embryos may be exposed to pesticides. Our objectives were to determine (i) if turtle eggs are capable of absorbing pesticides from treated soil, and (ii) if pesticide absorption rates can be predicted by their chemical and physical properties. Snapping turtle (Chelydra serpentina) eggs were incubated in soil that was treated with 10 pesticides (atrazine, simazine, metolachlor, azinphos-methyl, dimethoate, chlorpyrifos, carbaryl, endosulfan (I and II), captan, and chlorothalonil). There were two treatments, consisting of pesticides applied at application rate equivalents of 1.92 or 19.2 kg a.i/ha. Eggs were removed after one and eight days of exposure and analyzed for pesticides using gas chromatography coupled with a mass selective detector (GC-MSD) or high performance liquid chromatography (HPLC). Absorption of pesticides in eggs from soil increased with both magnitude and duration of exposure. Of the 10 pesticides, atrazine and metolachlor generally had the greatest absorption, while azinphos-methyl had the lowest. Chlorothalonil was below detection limits at both exposure rates. Our preliminary model suggests that pesticides having the highest absorption into eggs tended to have both low sorption to organic carbon or lipids, and high water solubility. For pesticides with high water solubility, high vapor pressure may also increase absorption. As our model is preliminary, confirmatory studies are needed to elucidate pesticide absorption in turtle eggs and the potential risk they may pose to embryonic development.     

Environmental pesticide distribution in horticultural and floricultural periurban production units

The environmental pesticide distribution on non-target systems (soil, drift and agricultural plastics) during the application step at small periurban production units, was studied in open field and greenhouses, for different crops (tomato, lettuce, broccoli, strawberry and flowers) using different pesticides (endosulfan, procymidone, chlorothalonil, chlorpyrifos and deltamethrin). In all cases, soil was the most exposed non-target system. For greenhouses, a general pesticide distribution was found of approximately 2/3 for crop, 1/4 for soil and 1/20 for plastic, of the total amount applied. In horticultural open fields, although the distribution was very dependent on the crop size and type, soil was also the most exposed non-target subsystem. Pesticide drift seems not to be significant in these production units, whilst pesticide accumulation on agricultural plastics reached up to 45% of the total applied, for polyethylene mulching in strawberry fields.     

Ammonia volatilization loss from surface applied livestock manure

Ammonia (NH₃) emission from livestock manures used in agriculture reduces N uptake by crops and negatively impacts air quality. This laboratory study was conducted to evaluate NH₃emission from different livestock manures applied to two soils: Candler fins sand (CFS; light-textured soil, pH 6.8 and field capacity soil water content of 70 g kg^{? 1}) from Lake Alfred, Florida and Ogeechee loamy sand (OLS; medium-textured soil, pH 5.2 and field capacity soil water content of 140 g kg^{? 1}) from Savannah, Georgia. Poultry litter (PL) collected from a poultry farm near Douglas, Georgia, and fresh solid separate of swine manure (SM) collected from a farm near Clinton, North Carolina were used. Each of the soil was weighed in 100 g sub samples and amended with either PL or SM at rates equivalent to either 0, 2.24, 5.60, 11.20, or 22.40 Mg ha^{? 1} in 1L Mason jars and incubated in the laboratory at field capacity soil water content for 19 days to monitor NH₃ volatilization. Results indicated a greater NH₃ loss from soils amended with SM compared to that with PL. The cumulative NH₃volatilization loss over 19 days ranged from 4 to 27% and 14 to 32% of total N applied as PL and SM, respectively. Volatilization of NH₃ was greater from light-textured CFS than that from medium-textured OLS. Volatilization loss increased with increasing rates of manure application. Ammonia volatilization was lower at night time than that during the day time. Differences in major factors such as soil water content, temperature, soil type and live stock manure type influenced the diurnal variation in volatilization loss of NH₃ from soils. A significant portion (> 50%) of cumulative NH₃ emission over 19 d occurred during the first 5–7 d following the application of livestock manures. Results of this study demonstrate that application of low rates of livestock manure (≤ 5.60 Mg ha^{? 1}) is recommended to minimize NH₃ emissions.     

Dissipation of chlorpyrifos in two soil environments of semi-arid India

The dissipation of chlorpyrifos (20 EC) at environment-friendly doses in the sandy loam and loamy sand soils of two semi-arid fields and the presence of pesticide residues in the harvested groundnut seeds, were monitored. The movement of chlorpyrifos through soil and its binding in the loamy sand soil was studied using 14C chlorpyrifos. Chlorpyrifos was moderately stable in both loamy sand and sandy loam soils, with half-life of 12.3 and 16.4 days, respectively. With 20 EC treatments the dissipation was slower for standing crop than seed treatment, indicative of the high degradation rates in the bioactive rhizosphere. In soil, 3,5,6-trichloro-2-pyridinol (TCP) was the principal breakdown product. Presence of 3,5,6-trichloro-2-methoxypyridine (TMP), the secondary metabolite, detected in the rhizospheric samples during this study, has not been reported earlier in field soils. The rapid dissipation of the insecticide from the soil post-application might have resulted from low sorption due to the alkalinity of the soil and its low organic matter content, fast topsoil dissipation possibly by volatilization and photochemical degradation, aided by the low water solubility, limited vertical mobility due to confinement of residues to the upper 15 cm soil layers and microbial mineralization and nucleophilic hydrolysis. Contrary to the reports of relatively greater mobility of its metabolites in temperate soils, TMP and TCP remained confined to the top 15 cm soil. The formation of bound residues (half-life 13.4 days) in the loamy sand soil was little and not "irreversible." A decline in bound residues could be correlated to decreasing TCP concentration. Higher pod yields were obtained from pesticide treated soils in comparison to controls. Post-harvest no pesticide residues were detected in the soils and groundnut seeds.     

Pesticide persistence and bound residues in soil--regulatory significance

The paper discusses key aspects of the European Union (EU) regulatory policy related to the persistence and bound residues of agricultural pesticide active substances in soil. This is examined in the context of the EU Authorisations Directive (91/414/EEC) which will gradually replace existing national systems of agricultural pesticide regulation within EU Member States. Discussion is concentrated on this directive, looking in particular at the Uniform Principles therein and the possible ways that these decision-making guidelines could be developed into a regulatory framework. The aim in this process of negotiated development is to identify any questions or data requirements that will be needed for persistent pesticides or soil bound residues, over and above those generally required for all compounds. The present EU regulatory position on soil non-extractable or bound residues is examined and possible future improvements to the system are described and discussed.     

Detection of residual organochlorine and organophosphorus pesticides in agricultural soil in Rio Verde region of San Luis Potosi,Mexico

Organochlorine pesticides were intensively used in Mexico from 1950 until their ban and restriction in 1991. However, the presence of these compounds is commonly reported in many regions of the country. The aim of the present study was to identify and quantify residual organochlorine and organophosphorus pesticides in agricultural soil in Rio Verde region, San Luis Potosi state, which has been identified as possibly polluted by pesticides. Composed samples from 24 zones covering an area of approximately 5,440 ha were analyzed. The most frequently found pesticides were p,p´-DDT followed by ,p,p´-DDE, heptachlor, endosulfan and γ-HCH whose frequency rates were 100, 91, 83 and 54%, respectively. The concentration of p,p´-DDT in the crops grown in these soils was in the following order: chili > maize > tomato > alfalfa. The results obtained in this study show that p,p´-DDT values are lower or similar to those found in other agricultural regions of Mexico. Methyl and ethyl parathion were the most frequent organophosphate pesticide detected in 100% and 62.5% of the samples with average concentrations of 25.20 and 47.48 μg kg^–1, respectively. More research is needed to establish the background levels of pesticides in agricultural soils and their potential ecological and human health effects in this region.     

Effects of thiobencarb in combinations with molinate and chlorpyrifos on selected soil microbial processes

The impact of pesticides, namely thiobencarb (TBC), molinate (MOL) and chlorpyrifos (CPF), on soil microbial processes was studied in two Australian soils. Substrate induced respiration (SIR), substrate induced nitrification (SIN) and phosphatases and chitinase enzymatic activities were assessed during a 30-day microcosm study. The pesticides were applied to soils at recommended rates either alone, or as binary mixtures with TBC. Soil samples were sampled at 5, 15 and 30 days after pesticide treatments. Substrate induced respiration was only transiently affected by pesticides in both soils. In contrast, the process of indigenous nitrification was affected by the presence of pesticides in both soils, especially when the pesticides were applied as binary mixtures. Substrate induced nitrification increased with pesticides in the Griffith soil (except with MOL+TBC after 5 days) whereas SIN values were non-significantly different to the control on the Coleambally soil. The binary mixtures of pesticides with TBC resulted in a decrease in SIN in both soils, but the effects disappeared within 30 days. The enzymatic activities were not consistently affected by pesticides, and varied with the soil and pesticides studied. This study showed that, when applied at recommended application rates, TBC, MOL, and CPF (individually or as binary mixtures), had little or only transitory effects on the functional endpoints studied. However, further investigations are needed to assess the effect on microbial densities and community structure despite the low disturbance to the functions noted in this work.