Effects of pesticides on soil enzymes: a review

The use of pesticides in agriculture has highly increased during the last 40 years to increase crop yields. However, today most pesticides are polluting water, soil, atmosphere and food. Pesticides are also impact soil enzymes, which are essential catalysts ruling the quality of soil life. In particular, the activity of soil enzymes control nutrient cycles, and, in turn, fertilization. Here, we review the effects of pesticides on the activity of soil enzymes in terrestrial ecosystems. Enzymes include dehydrogenase, fluorescein diacetate hydrolase, acid phosphatase, alkaline phosphatase, phosphatase, β-glucosidase, cellulase, urease and aryl-sulfatase. Those enzymes are involved in the cycles of carbon, nitrogen, sulfur and phosphorus. The main points of our analysis are (1) the common inhibition of dehydrogenase in 61 % of studies, stimulation of cellulase in 56 % of studies and no response of aryl-sulfatase in 67 % of studies. (2) Fungicides have mainly negative effects on enzymatic activities. (3) Insecticides can be classified into two groups, the first group represented by endosulfan having an overall positive impact while the second group having a negative effect. (4) Herbicides can be classified into two groups, one group with few positive effect and another group with negative effect.     

Combinatory chemical and biological approaches to investigate metal elements in agricultural runoff water

As part of a project studying the interactions between farming practices, soil erosion processes, and fate of agricultural pollutants into runoff waters, we conducted a pilot study to investigate the relationship between metal contents and metallothionein-2A (MT-2A) as a bioindicator of metal exposure. Runoff water samples were collected between May and November 1999 at the point of outlet of an elementary watershed located in the Paris basin. Selected metals (Al, As, Cd, Cr, Cu, Pb, Hg, Ni, and Zn) were analyzed using conventional techniques. In parallel, human T cells were exposed to water samples for 6 and 18 h and then cell viability and MT-2A gene expression were measured. Results show that among the 10 water samples tested, Al and Zn predominate (highest values = 4.9 and 2.6 microM, respectively), while other metals were below the microM level. Five out of 10 samples induced MT-2A gene expression (30-80% increase at 18 h) as compared with the control. When comparing MT-2A induction profile with metals contents, no obvious correlation was found, suggesting that additional components or parameters are involved. Finally, there was an apparent inverse relationship between Ca concentration and MT-2A gene induction. Although still preliminary, in the absence of longer monitoring, this study shows that MT-2A gene expression is a useful tool to complement chemical analysis in assessing metal elements in water. These combinatory approaches will be pursued and integrated in an ongoing watershed field research project.     

Spatial and temporal occurrence of N-nitrosamines in seven drinking water supply systems

The spatiotemporal presence of eight N-nitrosamines in the water of seven supply systems in Quebec considered to be susceptible to these emerging disinfection by-products was evaluated. This is the first study on the presence of N-nitrosamines in drinking water utilities in Quebec. Seven sampling campaigns were carried out at several sampling points in each of the systems over a period of 1 year. The results show that N-nitrosamines, primarily N-nitrosodimethylamine (NDMA), were not commonly detected in the water of the facilities under study (10 % of samples). The concentrations measured were lower than those reported in recent North American studies. None of the 195 samples taken exceeded the Ontario standard of 9 ng/L for NDMA (maximum value observed of 3.3 ng/L). N-nitrosomethylethylamine and N-nitrosopiperidine were detected once, with concentrations of 3.7 and 6.0 ng/L, respectively. Chloramination was identified as being the main risk factor regarding the presence of N-nitrosamines, but water quality and some operating parameters, in particular disinfectant residual, also seem to be related to their presence. NDMA concentrations at the end of the distribution systems were generally higher than water leaving the plant. No seasonal trends were observed for the formation of N-nitrosamines in the investigated supply systems. Finally, an association between the presence of N-nitrosamines and the levels of trihalomethanes and haloacetic acids was observed in some facilities.     

Dietary intake of hexabromocyclododecane diastereoisomers (α-, β-, and γ-HBCD) in the Belgian adult population

A study was performed to assess exposure of the Belgian population to HBCD diastereoisomers. Measurements of HBCD were performed by UPLC-MS/MS, on 45 composite samples from 5 major food groups: dairy (products), meat (products), eggs, fish (products) and a group of “other” products. The medium bound estimated average daily intake (EDI) of ΣHBCD in the Belgian population was 0.99 ng kg⁻¹ bw d⁻¹. The diastereoisomer contribution to the mean EDI showed a predominance of γ-HBCD at 67%, followed by α-HBCD at 25% and 8% for β-HBCD. These results are consistent with the pattern found in the two food groups contributing the most to the EDI: meat (products) and the group of “other” products. Anyway, it has to be noted that diastereomeric distribution of HBCD can change due to bioisomerisation in biological material. Levels of HBCD diastereoisomers found in Belgian food samples of animal origin were low in comparison with those found in other EU countries and the resulting EDI was substantially below the proposed thresholds.     

Secretion profiles of fungi as potential tools for metal ecotoxicity assessment: a study of enzymatic system in Trametes versicolor

The relationship between the expression of extracellular enzymatic system and a metal stress is scarce in fungi, hence limiting the possible use of secretion profiles as tools for metal ecotoxicity assessment. In the present study, we investigated the effect of Zn, Cu, Pb and Cd, tested alone or in equimolar cocktail, on the secretion profiles at enzymatic and protein levels in Trametesversicolor. For that purpose, extracellular hydrolases (acid phosphatase, β-glucosidase, β-galactosidase and N-acetyl-β-glucosaminidase) and ligninolytic oxidases (laccase, Mn-peroxidase) were monitored in liquid cultures. Fungal secretome was analyzed by electrophoresis and laccase secretion was characterized by western-blot and mass spectrometry analyses. Our results showed that all hydrolase activities were inhibited by the metals tested alone or in cocktail, whereas oxidase activities were specifically stimulated by Cu, Cd and metal cocktail. At protein level, metal exposure modified the electrophoretic profiles of fungal secretome and affected the diversity of secreted proteins. Two laccase isoenzymes, LacA and LacB, identified by mass spectrometry were differentially glycosylated according to the metal exposure. The amount of secreted LacA and LacB was strongly correlated with the stimulation of laccase activity by Cu, Cd and metal cocktail. These modifications of extracellular enzymatic system suggest that fungal oxidases could be used as biomarkers of metal exposure.     

Internal distribution of uranium and associated genotoxic damages in the chronically exposed bivalve Corbicula fluminea

Uranium (U) internal distribution and involved effects in the bivalve Corbicula fluminea have been studied after direct chronic exposure (90 d, 10 μg.L-1). U distribution was assessed at the subcellular level (Metal Rich Granules -MRG-, pellets and cytosol fractions) in two main organs of the bivalve (gills and visceral mass). Micro-localisation was investigated by TEM-EDX analysis in the gills epithelium. DNA damage in gill and hemolymph samples was measured by the Comet assay. The 90-d exposure period led to a significant increase of U concentration in gills over time (×5) and a large U quantity in subcellular granules in gills. Finally, a significant increase (×2) in DNA damage was noted in exposed gills and haemocytes. This study shows that the accumulation levels and consequently the potential toxicity cannot be successfully predicted only on the basis of concentration in water or in tissues and subcellular fractions after chronic exposure.     

A mesocosm approach for detecting stream invertebrate community responses to treated wastewater effluent

The discharge of wastewater from sewage treatment plants is one of the most common forms of pollution to river ecosystems, yet the effects on aquatic invertebrate assemblages have not been investigated in a controlled experimental setting. Here, we use a mesocosm approach to evaluate community responses to exposure to different concentrations of treated wastewater effluents over a two week period. Multivariate analysis using Principal Response Curves indicated a clear, dose-effect response to the treatments, with significant changes in macroinvertebrate assemblages after one week when exposed to 30% effluent, and after two weeks in the 15% and 30% effluent treatments. Treatments were associated with an increase in nutrient concentrations (ammonium, sulfate, and phosphate) and reduction of dissolved oxygen. These findings indicate that exposure to wastewater effluent cause significant changes in abundance and composition of macroinvertebrate taxa and that effluent concentration as low as 5% can have detectable ecological effects.     

Fate of metal-associated POM in a soil under arable land use contaminated by metallurgical fallout in northern France

Organic matter is a major metal-retaining constituent in soils. Among the diversity of organic components in soils, particulate organic matter (POM) accumulates large amounts of metals, but the fate of such metal-associated POM is unknown. We studied different POM size fractions and their corresponding mineral size-fractions isolated from the surface horizon of a soil affected by metallurgical fallout. Analyses of total and EDTA extractible metal contents performed on all size fractions demonstrated that with decreasing POM size, larger metal concentrations were observed but they were less extractable. Micromorphological study revealed the occurrence of opaque parts in decaying POM fragments and their individualization as fine, irregularly shaped opaque fragments in the soil matrix. This work suggested a mutual sequestration of metal pollutants and organic carbon as micro-meter sized, metal-enriched organic particles derived from POM, representing an original pathway for natural attenuation of risk related to metal contaminated soils.     

Aerobic metabolism and cardiac activity in the descendants of zebrafish exposed to pyrolytic polycyclic aromatic hydrocarbons

The increase of anthropogenic activities on coastal areas induces discharges of polycyclic aromatic hydrocarbons (PAHs) in aquatic ecosystem. PAH effects depend not only on their concentration and the way of contamination but also on the different developmental stages of the organism. Zebrafish were exposed to relevant concentration of pyrolytic PAHs from the first meal (i.e., 5-day post fertilization, dpf) to mature adults. Parental effect of this type of exposure was evaluated through the assessment of aerobic metabolic scope, cardiac frequency, and cardiac mRNA expression on larval and/or embryo progeny of contaminated fish. Our results suggest that cardiac frequency increased in larval descendants of fish exposed to the environmental concentration of pyrolytic PAHs (i.e., 5 ng.g^?1 of food), while a lack of effect on aerobic metabolism in 5 dpf larvae was highlighted. A surexpression of mRNA related to the cardiac calcium transporting ATPase atp2a2a, a protein essential for contraction, is in accordance with this increasing cardiac frequency. Even if cardiac development genes cmlc1 and tnnt2a were not affected at early life stages tested, complementary work on cardiac structure could be interesting to better understand PAHs action.