An indicator for effects of organic toxicants on lotic invertebrate communities: Independence of confounding environmental factors over an extensive river continuum

Distinguishing between effects of natural and anthropogenic environmental factors on ecosystems is a fundamental problem in environmental science. In river systems the longitudinal gradient of environmental factors is one of the most relevant sources of dissimilarity between communities that could be confounded with anthropogenic disturbances. To test the hypothesis that in macroinvertebrate communities the distribution of species' sensitivity to organic toxicants is independent of natural longitudinal factors, but depends on contamination with organic toxicants, we analysed the relationship between community sensitivity SPEAR_organic (average community sensitivity to organic toxicants) and natural and anthropogenic environmental factors in a large-scale river system, from alpine streams to a lowland river. The results show that SPEAR_organic is largely independent of natural longitudinal factors, but strongly dependent on contamination with organic toxicants (petrochemicals and synthetic surfactants). Usage of SPEAR_organic as a stressor-specific longitude-independent measure will facilitate detection of community disturbance by organic toxicants.     

Influence of fipronil compounds and rice-cultivation land-use intensity on macroinvertebrate communities in streams of southwestern Louisiana, USA

Laboratory tests of fipronil and its degradation products have revealed acute lethal toxicity at very low concentrations (LC50) of <0.5 microg/L to selected aquatic macroinvertebrates. In streams draining basins with intensive rice cultivation in southwestern Louisiana, USA, concentrations of fipronil compounds were an order of magnitude larger than the LC50. The abundance (rho=-0.64; p=0.015) and taxa richness (r2=0.515, p<0.005) of macroinvertebrate communities declined significantly with increases in concentrations of fipronil compounds and rice-cultivation land-use intensity. Macroinvertebrate community tolerance scores increased linearly (r2=0.442, p<0.005) with increases in the percentage of rice cultivation in the basins, indicating increasingly degraded stream conditions. Similarly, macroinvertebrate community-tolerance scores increased rapidly as fipronil concentrations approached about 1 microg/L. Pesticide toxicity index determinations indicated that aquatic macroinvertebrates respond to a gradient of fipronil compounds in water although stream size and habitat cannot be ruled out as contributing influences.     

Assuring the quality of data in the pesticide residue laboratory

Abstract

The importance of quality control procedures to the collection of pesticide residue data is discussed. The equipment requirements of an adequate, safe pesticide residue laboratory are presented. Equipment maintenance, personnel training, and preservation of samples is also reviewed. Appropriate objectives for an intra‐laboratory quality control program are outlined.     

Detection limits can influence the interpretation of pesticide monitoring data in Canadian surface waters

Water quality monitoring programs rely on residue data that are frequently left censored, due to some observations occurring below the Method Detection Limit (MDL). Our objective was to determine the influence the MDL has on the interpretation of pesticide residues in surface waters. Water samples from tributaries in southern and central Ontario were collected by Environment Canada from 2003 to 2008 and were analyzed for 27 pesticides, with MDLs that averaged 7.02 ng⁻¹ L (range 0.39-25.1 ng⁻¹ L). We then simulated MDLs ranging from 25 to 1700 ng⁻¹ L, to determine the impact this would have on the reporting of pesticide concentrations and detections. The mean number of pesticides detected simultaneously declined with increasing, i.e. less sensitive MDLs, from 5.02 pesticides (native MDL) to 0.08 pesticides detected (MDL < 1700 ng⁻¹ L). We compared the proportion of sites where pesticides were detected in surface waters under five MDL scenarios for 13 selected pesticides. The proportions decreased sharply with increasing MDLs. We calculated detection probabilities in an effort to compensate for higher MDLs using maximum likelihood; while adjusting for detection probabilities generally improved estimates of the presence of pesticides, as the MDLs increased the ability to compensate for detection probabilities deteriorated and became unviable at high MDLs. Depending on the method of substitution for observations below MDL (replacement with ½ × or 0 × MDL), the mean and median pesticide residues became increasingly over- and underestimated, respectively, at higher MDLs. Although monitoring programs that are focused on exceedences of water quality guidelines may not require low MDLs, the achievable goals of monitoring programs oriented towards other ecological and toxicological objectives may be limited by higher MDLs.     

Comparison of concentrations and stereoisomer ratios of mecoprop, dichlorprop and metolachlor in Ontario streams, 2006-2007 vs. 2003-2004

Mecoprop, dichlorprop and metolachlor concentrations and enantiomer signatures were determined in Ontario streams in 2006-2007 and compared to results from 2003 to 2004. Median concentrations of dichlorprop and metolachlor were not significantly different between the two campaigns, but mecoprop was higher in 2006-2007. Concentrations of mecoprop and dichlorprop in Lake Ontario surface water were 1-2 orders of magnitude lower than stream averages. Enantiomer fractions (EFs) > 0.5 of mecoprop in high-concentration stream water samples during 2006-2007 were related to replacement of racemic mecoprop by single (+) enantiomer mecoprop-P after 2004. EFs <0.5 in low-concentration samples suggested enantioselective degradation and/or interconversion. Metolachlor profiles were expressed as SF, the fraction of herbicidally active/(active + inactive) stereoisomers. Samples with higher concentrations of metolachlor had SFs similar to S-metolachlor which is enriched in the active stereoisomers. Low concentrations were associated with lower and more variable SFs, suggesting mixed input of racemic and S-metolachlor or stereoselective degradation.     

B-type esterases in the snail Xeropicta derbentina: an enzymological analysis to evaluate their use as biomarkers of pesticide exposure

The study was prompted to characterize the B-type esterase activities in the terrestrial snail Xeropicta derbentina and to evaluate its sensitivity to organophosphorus and carbamate pesticides. Specific cholinesterase and carboxylesterase activities were mainly obtained with acetylthiocholine (K_m = 77.2 mM; V_max = 38.2 mU/mg protein) and 1-naphthyl acetate (K_m = 222 mM, V_max = 1095 mU/mg protein) substrates, respectively. Acetylcholinesterase activity was concentration-dependently inhibited by chlorpyrifos-oxon, dichlorvos, carbaryl and carbofuran (IC50 = 1.35 × 10⁻⁵-3.80 × 10⁻⁸ M). The organophosphate-inhibited acetylcholinesterase activity was reactivated in the presence of pyridine-2-aldoxime methochloride. Carboxylesterase activity was inhibited by organophosphorus insecticides (IC50 = 1.20 × 10⁻⁵-2.98 × 10⁻⁸ M) but not by carbamates. B-esterase-specific differences in the inhibition by organophosphates and carbamates are discussed with respect to the buffering capacity of the carboxylesterase to reduce pesticide toxicity. These results suggest that B-type esterases in X. derbentina are suitable biomarkers of pesticide exposure and that this snail could be used as sentinel species in field monitoring of Mediterranean climate regions.     

Comparison of calculated evaporation rates of water droplets with those of pesticide droplets measured in a wind tunnel by Dennison and Wedding (1984)

Abstract

Calculations, based on Fuchs’ (1959) formula, of evaporation rates of water droplets freely falling through air are compared with those of water‐based pesticide droplets measured by Dennison and Wedding (1984) in a wind tunnel. Results indicate that calculations of evaporation rates of water droplets, are not significantly different from measurements of that of water‐based pesticide droplets under conditions of 20 °C and 20% relative humidity, but different under other measurement conditions.     

The use of a lacertid lizard as a model for reptile ecotoxicology studies: part 2--biomarkers of exposure and toxicity among pesticide exposed lizards

As part of a wider study examining the impacts of corn pesticides on lacertid lizards in north-western Portugal, we examined various physiological, biochemical, and histological biomarkers of exposure and effect among field populations of Podarcis bocagei. Biomarkers included body condition index, standard metabolic rate, locomotor performance, parasitization, glutathione oxidative pathways and related enzyme activity, lipid peroxidation and liver and testis histology. Few of the various biomarkers investigated provided statistically significant evidence of toxic effect. However, using a weight of evidence approach, we conclude that pesticides are affecting lizards living in the vicinity of pesticide exposed corn agriculture sites. Lizards from these locations present a profile of animals under metabolic stress with reduced condition indices, increased standard metabolic rate, lower incidence of hepatocyte vacuolation, altered iron metabolism, increased activation of GSH oxidation pathways, and even increased prevalence of hemoparasites.     

Determination of organochlorine and organophosphorus pesticide residues in low moisture,nonfatty products using a solid phase extraction cleanup and gas chromatography

Abstract

A multiresidue solid‐phase extraction (SPE) method for the isolation and subsequent gas Chromatographie determination of organochlorine and organophosphorus pesticide residues in low‐moisture, nonfatty products is described. Residues are extracted from samples with an acetonitrile/water mixture. Cleanup of the extract is performed using graphitized carbon black and anion exchange SPE columns, and analysis is performed by gas chromatography with Hall electrolytic conductivity and flame photometric detection. Recovery data was obtained by fortifying corn, oats and wheat with pesticides. The average recoveries were 79–123% for eight organochlorine and 51–122% for 28 organophosphorus pesticide residues. The limit of quantitation for chlorpyriphos was 0.05 ppm using the Hall electrolytic conductivity detector and <0.005 ppm using the flame photometric detector.     

Improving the knowledge of pesticide and nitrate transfer processes using age-dating tools (CFC, SF6, H) in a volcanic island (Martinique, French West Indies)

Numerous successful examples of CFC and SF₆ groundwater dating applications were recently published. However the proposed CFC/SF₆ method needs various hydrodynamic parameters that are not always available. In order to predict groundwater-quality trends in areas where the hydrogeological context is poorly known, a dating method using tritium, CFC and SF₆ was successfully implemented in Martinique. Hydrogeological understanding is limited in this volcanic island where groundwater contamination by pesticides and nitrate has been recently proven in various areas. A negative correlation was observed between nitrate concentrations and groundwater ages while pesticide contamination showed a more complex schema. Consequently the presence of old groundwater clearly explained the absence or low pesticide and nitrate concentrations in some areas. However a possible degradation of the water quality is to be feared in the future. In view of the relatively long transfer times and the complexity of the remobilization processes of solutes, the expected effects of any modifications in the use of fertilizers, or of changes in pesticide-use legislation, would take a long time to become apparent.     

Partitioning of Cd and Pb in the blood of European blackbirds (Turdus merula) from a smelter contaminated site and use for biomonitoring

Blood composition is commonly measured to assess exposure to and effects of metals on birds. In most of passerine species, only small volumes of blood may be sampled safely (<500 μL), which limit the measure of several markers of health status and chemical residues. Here, we documented the partitioning of Cd and Pb in the blood of European Blackbirds Turdus merula in order to propose usable relationships between whole blood concentrations (for which toxicological benchmarks exist) and those measured in the erythrocytes. Sixty-two blackbirds were trapped along a pollution gradient (smelter of Metaleurop Nord, Northern France). Blood was sampled and Cd and Pb concentrations were measured both in whole blood and in the erythrocytes only. Birds coming from the most contaminated sites exhibited high residues for both Cd and Pb. We assessed that 73% and 99% of Cd and Pb, respectively, were associated to erythrocytes. Strong linear relationships, that were not influenced by neither the age nor the sex, were established between whole blood residues and those of erythrocytes for Cd and Pb (adj-R² = 0.78 and 0.93, respectively). Present findings are promising to optimize the use of small blood samples in order to investigate several responses relative to wildlife health status.     

The use of nanovermiculite catalyst in the study of removal of the organic load and degradation of atrazine via ozone process in RPB reactor

Abstract

The main objective of this study is the degradation of a synthetic solution of atrazine by a modified vermiculite catalyzed ozonation, in a rotating packed bed (RPB) reactor. A 0.5?L RPB reactor was used to perform the experiments, using a Central Composite Design (CCD) response surface to construct the quadratic model based on the factors: pH, catalyst concentration and reactor rotation frequency. The response variable was the removal of the organic load measured in terms of Chemical Oxygen Demand (COD). After the complete quadratic model was constructed through the response surface, the COD degradation process had an optimal removal of 41% under the following conditions: pH 8.0, rotation of 1150?rpm and catalyst concentration 0.66?g L^?1.     

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.     

A functional perspective on the analysis of land use and land cover data in ecology

Assessments of large-scale changes in habitat are a priority for management and conservation. Traditional approaches use land use and land cover data (LULC) that focus mostly on “structural” properties of landscapes, rather than “functional” properties related to specific ecological processes. Here, we contend that designing functional analyses of LULC can provide important and complementary information to traditional, structural analyses. We substantiate this perspective with an example of functional changes in habitat due to industrial anthropogenic footprints in Alberta’s boreal forest, where there has been little overall forest loss (~ 6% structural change), but high levels of functional change (up to 93% functional change) for species’ habitat, biodiversity, and wildfire ignition. We discuss the methods needed to achieve functional LULC analyses, when they are most appropriate to add to structural assessments, and conclude by providing recommendations for analyses of LULC in a future of increasingly high-resolution, dynamic remote sensing data.Electronic supplementary materialThe online version of this article (10.1007/s13280-020-01434-5) contains supplementary material, which is available to authorized users.     

Cholinesterase characterization in Corbicula fluminea and effects of relevant environmental contaminants: A pesticide (chlorfenvinphos) and a detergent (SDS)

This study characterizes the cholinesterasic forms present in the bivalve Corbicula fluminea, through the analysis of differential affinity towards various substrates and inhibitors. This approach also permitted the validation of cholinesterase inhibition in the mentioned species for monitoring purposes by evaluating the inhibitory activity of a detergent (SDS) and a pesticide (chlorfenvinphos), both in vitro and in vivo. The cholinesterasic form present in the tissues of C. fluminea showed intermediate properties in terms of its relation with substrates and inhibitors. Furthermore, it was not inhibited by the detergent SDS under any of the test conditions, but was clearly inhibited by the selected organophosphate. The data show clearly that the main cholinesterasic form in C. fluminea is responsive to the organophosphate chlorfenvinphos, thus supporting the use of this biomarker for the environmental monitoring of specific contaminants such as anticholinesterasic pesticides. Despite not being commonly attained in the wild, the levels of chlorfenvinphos required to elicit a significant ChE inhibition were only one order of magnitude above actual values of aquatic contamination by this pesticide.     

The use of experimental data and their uncertainty for assessing ozone photochemistry in the Eastern Iberian Peninsula

Observation-based methods are useful tools to explore the sensitivity of ozone concentrations to precursor controls. With the aim of assessing the ozone precursor sensitivity in two locations: Paterna (suburban) and Villar del Arzobispo (rural) of the Turia river basin in the east of Spain, the photochemical indicator O₃/NO_y and the Extent-of-Reaction (EOR) parameter have been calculated from field measurements. In Paterna, the O₃/NO_y ratio varied from 0 to 13 with an average value of 5.1 (SD 3.2), whereas the averaged value for the EOR was 0.43 (SD 0.14). In Villar del Arzobispo, the O₃/NO_y ratio changed from 5 to 30 with a mean value of 13.6 (SD 4.7) and the EOR gave an averaged value of 0.72 (SD 0.11). The results show two different patterns of ozone production as a function of the location. The suburban area shows a VOC-sensitive regime whereas the rural one shows a transition regime close to NO_x-sensitive conditions. No seasonal differences in these regimes are observed along the monitoring campaigns. Finally, an analysis of the influence of the measurement quality of NO_y, NO_x and O₃ on the uncertainty of the O₃/NO_y ratio and the EOR was performed showing that the uncertainty of O₃/NO_y is not dependent on either its value or the individual values of O₃ and NO_y but just on the quality of O₃ and NO_y measurements. The maximum uncertainty is 26% as long as the combined uncertainties of O₃ and NO_y remain below the 7.5%. The case of the EOR is different and its uncertainty depends on both the value of the EOR parameter and the individual concentration values of NO_y and NO_x. The uncertainty of the EOR estimation can be very high (>200%) if the combined uncertainties of both NO_y and NO_x are high (>7.5%), or especially, if u(NO_y) and u(NO_x) differ considerably from each other (>3.5%).     

Behaviour of pharmaceuticals in spiked lake sediments - effects and interactions with benthic invertebrates

The behaviour and effects of atorvastatin (ATO), carbamazepine (CBZ), and 17α-ethinylestradiol (EE2) were investigated in spiked lake sediments, at concentrations up to 56.5 mg kg⁻¹ dry weight (dw), with the benthic invertebrates Chironomus dilutus and Hyalella azteca. Desorption constants were calculated in the presence and absence of animals, using linear isotherms, yielding K_d values of 28.2, 189.0 and 125.1 L kg⁻¹ (ATO), 73.7, 201.7 and 263.2 L kg⁻¹ (CBZ), and 114.9, 114.2 and 519.2 L kg⁻¹ (EE2) for C. dilutus, H. azteca, and without animals, respectively. For ATO and CBZ, K_d values were smaller in the presence of C. dilutus, indicating greater desorption to the overlying water from bioturbation, which is consistent with the predominantly benthic occurrence of C. dilutus compared to H. azteca. In contrast, due to its greater hydrophobicity, bioturbation did not significantly affect desorption of EE2. No significant toxicity was observed, indicating decreased bioavailability of the chemicals sorbed to sediments compared with water-only toxicity assays.