SPEAR indicates pesticide effects in streams - Comparative use of species- and family-level biomonitoring data

To detect effects of pesticides on non-target freshwater organisms the Species at risk (SPEAR_pesticides) bioindicator based on biological traits was previously developed and successfully validated over different biogeographical regions of Europe using species-level data on stream invertebrates. Since many freshwater biomonitoring programmes have family-level taxonomic resolution we tested the applicability of SPEAR_pesticides with family-level biomonitoring data to indicate pesticide effects in streams (i.e. insecticide toxicity of pesticides). The study showed that the explanatory power of the family-level SPEAR(fm)_pesticides is not significantly lower than the species-level index. The results suggest that the family-level SPEAR(fm)_pesticides is a sensitive, cost-effective, and potentially European-wide bioindicator of pesticide contamination in flowing waters. Class boundaries for SPEAR_pesticides according to EU Water Framework Directive are defined to contribute to the assessment of ecological status of water bodies.     

The effects of conservation tillage practices on benthic invertebrate communities in headwater streams in southwestern Ontario, Canada

Samples of benthic invertebrates from four pairs of streams in southwestern Ontario collected monthly from May through August 1991, and once during the subsequent autumn and winter, demonstrated that conservation tillage practices have a remedial effect on the water quality of adjacent streams as indicated by biotic, rather than physical or chemical, parameters. One stream of each pair drained a basin under conventional tillage (CONV, mainly mouldboard ploughing), the other primarily under conservation tillage (CONS). The paired drainage basins were otherwise similar to one another in type of crops grown, as well as size, topography, soils and hydrology. CONS streams yielded a greater variety of Insecta but fewer taxa of Mollusca, Annelida and Crustacea than did samples from CONV streams. Both kick-net and Surber samples from CONS streams yielded significantly more taxa, more kinds of Ephemeroptera, Plecoptera and Trichoptera, and lower Hilsenhoff Biotic Index scores than did samples from CONV streams. Kick samples from CONS streams were significantly more similar to expected reference communities in overall taxonomic composition. Surber samples from CONS streams contained significantly larger numbers of invertebrates. The relatively greater abundances of infaunal species, especially Tubificidae and Chironomini, in CONV streams suggest greater accumulation of fine sediment particles. Conditions during low flow appear to have the greatest influence on the composition of benthic invertebrate communities. The results of the study indicate that conservation tillage practices have a beneficial effect on the quality of surface waters.     

Fate and distribution of fipronil on companion animals and in their indoor residences following spot-on flea treatments

Use of fipronil {5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile CAS 120068–37-3} topical pet products on dogs and cats introduces low level residues into residences. Distribution and fate studies of fipronil on pets and in residences were performed to evaluate potential determinants of human exposure. Fipronil, desulfinyl fipronil, fipronil sulfone and fipronil sulfide were measured on hair clippings and brushed hair. The derivatives usually represented <10% of fipronil applied. Cotton gloves worn over impervious nitrile gloves, cotton cloths placed indoors in locations frequented by pets, and cotton socks worn by residents as direct dosimeters collected fipronil and its derivatives listed above in low amounts during 4-week study periods. Subsequent acid hydrolysis urine biomonitoring did not reveal significant excretion of biomarkers at ppb levels. The human exposure potential of fipronil is low relative to levels of health concern.     

Assessing supercritical fluid extraction for the analysis of fipronil,kresoxim-methyl,acrinathrin, and pyridaben residues in melon

An analytical method, using supercritical fluid extraction (SFE), was assessed for residue analysis of the insecticides fipronil, acrinathrin and pyridaben and the fungicide kresoxim-methyl in melons. Extraction conditions were optimized on glass beads, as inert material, evaluating different pressures, temperatures, and CO₂ volumes. Also, the extractability of pesticides from hydromatrix and anhydrous magnesium sulfate was evaluated. Both adsorbents were evaluated for the preparation of SFE-spiked melon samples. Extractions of fortified samples were done using 20 mL of CO₂, 300 atm, and 50°C. Different extraction conditions, including the addition of water and methanol as a static modifier, were used to assess the extractability of these pesticides, and the addition of methanol was demonstrated to improve the extraction of all the studied pesticides.     

Effect of fipronil on biogas production performance during anaerobic digestion of chicken manure and corn straw

Fipronil is a broad-spectrum insecticide that has a good control effect on pests of commercial poultry. Although many studies have reported the environmental fate of fipronil, the influence of residual fipronil in poultry waste on biogas production has not been further explored yet. In this article, an experimental comparative study on anaerobic digestion (AD) of chicken manure (CM) and corn straw (CS) with different fipronil concentrations (FCs) was carried at 8% of total solid (TS) and mid-temperature (35?±?1)°C. The results showed that fipronil had a significant effect on biogas production during AD of CM and CS. When the FC is at a low level (≤10?mg·kg^?1), the biogas production rate is increased and the digestion period was shortened, while higher FC (≥ 20?mg·kg^?1) showed an inhibitory effect. During the monitoring of enzyme activity, low FC showed no significant effect on cellulase and saccharase, but the urease activity increased in the early stage. High FC showed inhibition of activity of cellulase and urease, but the saccharase activity was significantly inhibited until FC reached 40?mg·kg^?1. This study also confirms that the environment in anaerobic digester is favorable for the degradation of fipronil, and its half-life is about 15.83?days.     

Effects of intense agricultural practices on heterotrophic processes in streams

In developed countries, changes in agriculture practices have greatly accelerated the degradation of the landscape and the functioning of adjacent aquatic ecosystems. Such alteration can in turn impair the services provided by aquatic ecosystems, namely the decomposition of organic matter, a key process in most small streams. To study this alteration, we recorded three measures of heterotrophic activity corresponding to microbial hydrolasic activity (FDA hydrolysis) and leaf litter breakdown rates with (k_c) and without invertebrates (k_f) along a gradient of contrasted agricultural pressures. Hydrolasic activity and k_f reflect local/microhabitat conditions (i.e. nutrient concentrations and organic matter content of the sediment) but not land use while k_c reflects land-use conditions. k_c, which is positively correlated with the biomass of Gammaridae, significantly decreased with increasing agricultural pressure, contrary to the taxonomic richness and biomass of Trichoptera and Plecoptera. Gammaridae may thus be considered a key species for organic matter recycling in agriculture-impacted streams.     

Isonychia spp. and macroinvertebrate community responses to stressors in streams utilizing the benthic in situ toxicity identification evaluation (BiTIE) method

Exposures of caged organisms in situ have proven to be a useful way to improve exposure realism and link to stressor effects in aquatic assessments of hazard or risk. A novel cage system, the benthic in situ toxicity identification evaluation (BiTIE), was developed for benthic macroinvertebrates (surrogate species, resident populations and communities) to separate low and high flow effects, and major chemical classes of stressors in streams. Three resin types were used to separate the chemical stressors in the streams Honey Creek and Little Beavercreek, Ohio, USA: Dowex Optipore (non-polar organics), zeolite (ammonia), and polywool (control). Isonychia spp. sensitivity was compared to Chironomus tentans, and no significant differences were found (p>0.05). Isonychia spp. growth (length) showed a stressor response in the zeolite treatments, and community testing revealed improved metric responses in the Dowex treatments. The BiTIE chamber system demonstrated stressor-response relationships using sublethal and multimetric endpoints.     

Wetlands as principal zones of methylmercury production in southern Louisiana and the Gulf of Mexico region

It is widely recognized that wetlands, especially those rich in organic matter and receiving appreciable atmospheric mercury (Hg) inputs, are important sites of methylmercury (MeHg) production. Extensive wetlands in the southeastern United States have many ecosystem attributes ideal for promoting high MeHg production rates; however, relatively few mercury cycling studies have been conducted in these environments. We conducted a landscape scale study examining Hg cycling in coastal Louisiana (USA) including four field trips conducted between August 2003 and May 2005. Sites were chosen to represent different ecosystem types, including: a large shallow eutrophic estuarine lake (Lake Pontchartrain), three rivers draining into the lake, a cypress-tupelo dominated freshwater swamp, and six emergent marshes ranging from a freshwater marsh dominated by Panicum hemitomon to a Spartina alterniflora dominated salt marsh close to the Gulf of Mexico. We measured MeHg and total Hg (THg) concentrations, and ancillary chemical characteristics, in whole and filtered surface water, and filtered porewater. Overall, MeHg concentrations were greatest in surface water of freshwater wetlands and lowest in the profundal (non-vegetated) regions of the lake and river mainstems. Concentrations of THg and MeHg in filtered surface water were positively correlated with the highly reactive, aromatic (hydrophobic organic acid) fraction of dissolved organic carbon (DOC). These results suggest that DOC plays an important role in promoting the mobility, transport and bioavailability of inorganic Hg in these environments. Further, elevated porewater concentrations in marine and brackish wetlands suggest coastal wetlands along the Gulf Coast are key sites for MeHg production and may be a principal source of MeHg to foodwebs in the Gulf of Mexico. Examining the relationships among MeHg, THg, and DOC across these multiple landscape types is a first step in evaluating possible links between key zones for Hg(II)-methylation and the bioaccumulation of mercury in the biota inhabiting the Gulf of Mexico region.     

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.     

Projecting Climate Change Effects on Forest Net Primary Productivity in Subtropical Louisiana,USA

This study projected responses of forest net primary productivity (NPP) to three climate change scenarios at a resolution of 5 km × 5 km across the state of Louisiana, USA. In addition, we assessed uncertainties associated with the NPP projection at the grid and state levels. Climate data of the scenarios were derived from Community Climate System Model outputs. Changes in annual NPP between 2000 and 2050 were projected with the forest ecosystem model PnET-II. Results showed that forest productivity would increase under climate change scenarios A1B and A2, but with scenario B1, it would peak during 2011–2020 and then decline. The projected average NPP under B1 over the years from 2000 to 2050 was significantly different from those under A1B and A2. Forest NPP appeared to be primarily a function of temperature, not precipitation. Uncertainties of the NPP projection were due to large spatial resolution of the climate variables. Overall, this study suggested that in order to project effects of climate change on forest ecosystem at regional level, modeling uncertainties could be reduced by increasing the spatial resolution of the climate projections.     

Residences with anomalous soil concentrations of dioxin-like compounds in two communities in Michigan, USA: a case study

Most contamination of residential property soil with dioxin-like compounds occurs as a result of proximity to industrial activity that produces such compounds and, outside the industrially impacted zone, the soil concentrations are at background levels. However, as part of the University of Michigan Dioxin Exposure Study, residential properties in the lower peninsula of Michigan, USA, were identified that were located far enough from known sources of these compounds that the soil concentrations should have been at background levels and yet the toxic equivalent (TEQ) of some properties' soil was greater than 2.5 standard deviations above the mean background level. In the three cases presented here from Midland/Saginaw Counties, the anomalously high-TEQ values were primarily due to the presence of polychlorinated dibenzofurans. Based on interviews with the residents and a comparison of soil congener profiles, it was deduced that these values resulted from anthropogenic soil movement from historically contaminated areas. In the cases from Jackson/Calhoun Counties, the unusually high-TEQ values were primarily due to polychlorinated biphenyls. In the case profiled here, it appears that the soil became contaminated through sandblasting to remove paint from the swimming pool. This study identified two mechanisms for soil contamination outside zones of industrial impact; thus, an assumption of background levels of soil contamination outside industrial zones may not be valid.     

Carbendazim dissipation in the biomixture of on-farm biopurification systems and its effect on microbial communities

The impact of repeated carbendazim (CARB) applications on the extent of CARB dissipation, the microbial diversity, the community level physiological profile (CLPP), and the enzymatic activity within the biomixture of an on-farm biopurification system was evaluated. After three successive CARB applications, the CARB dissipation efficiency was high; the efficiency of dissipation was 87%, 94% and 96% after each application, respectively. Although microbial enzymatic activity was affected significantly by CARB application, it could recover after each CARB pulse. Likewise, the numbers of cultivable bacteria, fungi and actinomycetes (as measured in CFUs) were slightly affected by the addition of CARB, but the inhibitory effect of the pesticide application was temporary. Denaturing gradient gel electrophoresis (DGGE) and Biolog Ecoplate assays demonstrated that the microbial populations remained relatively stable over time when compared to the control. The results obtained herein therefore demonstrate the high dissipation capacity of this biomixture and highlight the microbiological robustness of this biological system.     

Biological water quality assessment of running waters based on macroinvertebrate communities: history and present status in Europe

This paper reviews the history and development of biological water quality assessment using macroinvertebrates in Europe, and critically evaluates each of the principal approaches used. As the biotic approach incorporates the most highly regarded features of the saprobic and diversity approaches, it has received the most attention in recent years. Most modern biotic index and score systems have evolved from the Trent Biotic Index, through a series of refinements and adaptations (i.e. the Extended Biotic Index, Chandler's Score, Indice Biotique) into the two modern systems. These methods are the Biological Monitoring Working Party System, used mainly in Great Britain, and the Belgian Biotic Index Method. The results of these techniques are now influencing policy decisions concerning surface water management in Europe, where macroinvertebrate community assessment are being used as a planning tool for managing water uses, for ambient monitoring, and for evaluating the effectiveness of pollution control measures. New research directions aimed at improving the performance of bioassessment techniques are being explored. These include defining reference communities based on stream typology which can then be used to set water quality objectives, and applying these methods to the assessment of toxic pollution.     

Occurrence and treatment of arsenic in groundwater and soil in northern Mexico and southwestern USA

This review focuses on the occurrence and treatment of arsenic (As) in the arid region of northern Mexico (states of Chihuahua and Coahuila) and bordering states of the southwestern US (New Mexico, Arizona, and Texas), an area known for having high As concentrations. Information assembled and assessed includes the content and probable source of As in water, soil, and sediments and treatment methods that have been applied in the area. High As concentrations were found mainly in groundwater, their source being mostly from natural origin related to volcanic processes with significant anthropogenic contributions near mining and smelting of ores containing arsenic. The affinity of As for solid phases in alkaline conditions common to arid areas precludes it from being present in surface waters, accumulating instead in sediments and shifting its threat to its potential remobilization in reservoir sediments and irrigation waterways. Factors such as oxidation and pH that affect the mobility of As in the subsurface environment are mentioned. Independent of socio-demographic variables, nutritional status, and levels of blood lead, cognitive development in children is being affected when exposed to As. Treatments known to effectively reduce As content to safe drinking water levels as well as those that are capable of reducing As content in soils are discussed. Besides conventional methods, emergent technologies, such as phytoremediation, offer a viable solution to As contamination in drinking water.     

Levels and source apportionment of volatile organic compounds in southwestern area of Mexico City

Thirteen volatile organic compounds (VOCs) were quantified at three sites in southwestern Mexico City from July 2000 to February 2001. High concentrations of different VOCs were found at a Gasoline refueling station (GS), a Condominium area (CA), and at the University Center for Atmospheric Sciences (CAS). The most abundant VOCs at CA and CAS were propane, n-butane, toluene, acetylene and pentane. In comparison, at GS the most abundant were toluene, pentane, propane, n-butane, and acetylene. Benzene, a known carcinogenic compound had average levels of 28, 35 and 250 ppbC at CAS, CA, and GS respectively. The main contributing sources of the measured VOCs at CA and CAS were the handling and management of LP (Liquid Propane) gas, vehicle exhaust, asphalt works, and use of solvents. At GS almost all of the VOCs came from vehicle exhaust and fuel evaporation, although components of LP gas were also present. Based on the overall results possible abatement strategies are discussed.     

Effect of triazophos,fipronil and their mixture on miRNA expression in adult zebrafish

MicroRNA (miRNA) plays a crucial role in gene expression regulation. However, no data are available on change of miRNA expression of zebrafish (Danio rerio) after treatment with pesticides. We evaluated the effect of fipronil (5-amino-1-[2, 6-dichloro-4-(trifluoromethyl) phenyl]-4-[(trifluoromethyl) sulfinyl]-1H-pyrazole-3-carbonitrile) and triazophos (3-(O, O-diethyl)-1-phenyl thiophosphoryl-1, 2, 4-triazol) and their mixture on miRNA expression in zebrafish. MiRNA expression profiles in zebrafish were altered after treatment with these chemicals. An association between these chemicals and the expression of 21 miRNAs was found 96 h after treatment. Among them, 14 miRNAs were differentially expressed due to the treatments with fipronil, triazophos and their mixture; 5 miRNAs showed altered expression level after treatment with formulations of these chemicals; miR-29b and miR-738 were differentially expressed after treatment with adjuvants. MiRNAs might present a novel toxicological response that could be used as a toxicological biomarker and have a different direction for future investigations of their association with miRNAs involved in chemical related diseases.     

Perfluorinated compounds in whole fish homogenates from the Ohio, Missouri, and Upper Mississippi Rivers, USA

A method for the analysis of 10 perfluorinated compounds (PFCs) in whole fish homogenate is presented and applied to 60 fish samples collected from the Ohio, Missouri, and upper Mississippi Rivers in 2005. Method accuracy ranged between 86 and 125% with limits of quantitation between 0.2 and 10 ng/g wet weight. Intra- and inter-batch precision was generally ±20%. Perfluorooctane sulfonate (PFOS) was the predominant compound identified in these samples, contributing over 80% of total PFC composition in the fish from these rivers, with median PFOS concentrations of 24.4, 31.8, and 53.9 ng/g wet wt in the Missouri, Ohio, and Mississippi Rivers, respectively. Median PFOS levels were significantly (p = 0.01) elevated in piscivorous fish (88.0 ng/g) when compared with non-piscivorous fish (15.9 ng/g). The 10 samples with PFOS concentrations above 200 ng/g were broadly scattered across all three rivers, providing evidence of the widespread presence of this compound in these US waterways.     

Influence of benomyl and prometryn on the soil microbial activities and community structures in pasture grasslands of Slovakia

The effects of pesticides (a herbicide and a fungicide) on the microbial community structure and their activity were analyzed in soil from four alpine pasture grasslands in Slovakia. Specifically, the effects of the herbicide, Gesagard (prometryn active ingredient), and fungicide, Fundazol 50 WP (benomyl active ingredient), on the microbial respiration activity (CO₂ production), the numbers of selective microbial physiological groups (CFU.g^?1) and the structure (relative abundance) of soil microbial communities [(phospholipid fatty acid (PLFA)] were analyzed under controlled laboratory conditions. All treatments including the treatments with pesticides increased (statistically significantly) the production of CO₂ in all fields during 21 days of incubation and posed a statistically insignificant negative influence on the numbers of the observed physiological groups of microorganisms. The significantly negative influence was evaluated only in the numbers of two physiological groups; spores of bacteria utilizing organic nitrogen and bacteria, and their spores utilizing inorganic nitrogen. A shift in the microbial composition was evident when the PLFA patterns of samples from different sites and treatments were compared by the Principal Component Analysis (PCA). According to the second component PCA 2 (15.95 %) the locations were grouped into two clusters. The first one involved the Donovaly and Dubakovo sites and the second one contained the Velka Fatra and Mala Fatra locations. The PLFA composition of the soils showed important changes after the treatment with pesticides according to PCA 1 (66.06 %). Other treatments had not had a significant effect on the soil microbial community with the exception of the population of fungi. The lower relative abundance (significant effect) of Gram-positive bacteria, actinomycetes and general group of bacteria were determined in samples treated by the herbicide Gesagard. The application of fungicide Fundazol decreased (statistically significantly) the relative abundance of actinomycetes and general group of bacteria and paradoxically increased the population of fungi.     

Degradation of benomyl, picloram, and dicamba in a conical apparatus by zero-valent iron powder

Reduction of some pesticides (benomyl, picloram, and dicamba) was studied in an aerobic batch conical pilot system to investigate the disappearance of these pesticides on contact with iron powder (20 g/l, 325-mesh). Aqueous buffered solutions of the compounds were added to the system followed by zero-valent iron powder (ZVIP), and the decline in the pesticide concentrations was monitored over time. HPLC analyses show a complete disappearance of picloram (1.20 mg/l) after 20 min of reaction. Benomyl (1.00 mg/l) and dicamba (1.25 mg/l) disappear after 25 and 40 min, respectively. The t₅₀ values ranged from 3 to 5.5 min, and were about slightly less than the t_1/2 values reported when the log of the relative HPLC peak area was plotted versus time, where the relative peak area was calculated by dividing the measured peak area by the initial peak area. Pathways for the degradation of the studied pesticides by ZVIP are proposed.     

Paper electrophoretic separations of some common pesticides : Determination of monocrotophos,rogor and malathion in soil samples

Abstract

Paper electrophoretic movements of a number of pesticides belonging to organophosphorus, organochlorine and pyethroid groups in various acid background electrolytes have been studied. The effect of pH and pKa of the acids on the movement of these pesticides have also been studied. It has been observed that the movement of most of the pesticides is enhanced with increase in the degree of ionisation of the acids (pKa) studied as background electrolytes. The movement also increases with increase in the pH of acids. On the basis of differential movement of pesticides towards cathode and anode, a number of separations have been achieved from binary mixtures. Monocrotophos, rogor and malathion have been determined quantitatively (28.6 ‐ 29.2 μg) in alcoholic extracts of soil samples.