Soil amendments reduce PFAS bioaccumulation in Eisenia fetida following exposure to AFFF-impacted soil.

The efficacy of RemBind® 300 to immobilize per- and polyfluoroalkyl substances (PFAS) in aqueous film forming foam (AFFF)-impacted soil (∑28 PFAS 1280-8130 ng g-1; n = 8) was assessed using leachability (ASLP) and bioaccumulation (Eisenia fetida) endpoints as the measure of efficacy. In unamended soil, ∑28 PFAS leachability ranged from 26.0 to 235 µg l-1, however, following the addition of 5% w/w RemBind® 300, ∑28 PFAS leachability was reduced by > 99%. Following exposure of E. fetida to unamended soil, ∑28 PFAS bioaccumulation ranged from 18,660-241,910 ng g-1 DW with PFOS accumulating to the greatest extent (15,150-212,120 ng g-1 DW). Biota soil accumulation factors (BSAF) were significantly (p < 0.05) higher for perfluoroalkyl sulfonic acids (PFSA; 13.2-50.9) compared to perfluoroalkyl carboxylic acids (PFCA; 1.2-12.7) while for individual PFSA, mean BSAF increased for C4 to C6 compounds (PFBS: 42.6; PFPeS: 52.7; PFHxS: 62.4). In contrast, when E. fetida were exposed to soil amended with 5% w/w RemBind® 300, significantly lower PFAS bioaccumulation occurred (∑28 PFAS: 339-3397 ng g-1 DW) with PFOS accumulation 23-246 fold lower compared to unamended soil. These results highlight the potential of soil amendments for reducing PFAS mobility and bioavailability, offering an immobilization-based risk management approach for AFFF-impacted soil.

Acute toxicity of the insecticide methyl parathion and its hydrolytic product p-nitrophenol to the native Australian cladoceran Daphnia carinata.

The toxicity of an organophosphorus (OP) insecticide, methyl parathion (MP), and its hydrolysis product, p-nitrophenol (PNP), to the native Australian cladoceran species, Daphnia carinata, was assessed. Both MP and PNP were stable in cladoceran water during the test period. D. carinata was sensitive to both MP and PNP; however, the parent compound was more toxic than its metabolite. This is the first study that demonstrated the acute toxicity of MP and PNP towards an Australian daphnid species. The present investigation emphasizes the need for including the native taxa as non-target test organisms while evaluating the toxicity of environmental pollutants.

Sorption of 14C-carbofuran in Austrian soils: evaluation of fate and transport of carbofuran in temperate regions.

Carbofuran is an anticholinesterase carbamate commonly used as an insecticide, nematicide and acaricide in agricultural practice throughout the world. However, data on its sorption in temperate soils from Europe is limited. Laboratory studies were conducted to determine the adsorption of carbofuran on three distinct Austrian soils using batch experiments and radiometric techniques. Carbofuran adsorption capacity of the soils was found to be low in the three soils tested and showed to be related to the soils clay and organic carbon contents. The pesticide presented linear adsorption isotherms in all of the three soils. Due to the low sorption of carbofuran in the soils tested and to its high water solubility, there is a risk of migration to water bodies through run off and consequent negative effects on aquatic organisms and soil biota.

Sorption and mobility of 14C-fenamiphos in Brazilian soils.

Although fenamiphos is widely used as an insecticide and nematicide in bowling greens and agriculture, information on its sorption in tropical soils is limited. In this study, mobility, sorption, and desorption dynamics of 14C-fenamiphos in three contrasting Brazilian soils were examined both in batch and column experiments. Fenamiphos sorption coefficients (K d ) were 2.33, 3.86, and 3.9 L kg-1 for the three soils tested. The insecticide exhibited linear adsorption isotherms in all the three soils, and desorption was in a range of 30-40% during a 72-h period. With its low mobility, fenamiphos did not percolate through the soil profile even after 48 h. However, there is a risk of leaching to water bodies due to runoff because of its high solubility in water. In view of the fact that fenamiphos and its oxidation products are highly toxic to aquatic invertebrates and could affect the soil microbial activities even at low concentrations, the present information is of great importance in risk assessment of fenamiphos in the environment.

Toxicity and transformation of insecticide fenamiphos to the earthworm Eisenia fetida.

This study was conducted to investigate the toxicity of the organophosphate insecticide fenamiphos to earthworms (Eisenia fetida) under laboratory conditions. Earthworms were exposed to soils differing in their physico-chemical properties spiked with fenamiphos at concentrations ranging from 10 to 200 mg kg(-1) for a period of 4 weeks. Residues of fenamiphos and its metabolites were determined in both soils and earthworms after 4 weeks of pesticide exposure. Fenamiphos was degraded faster in the alkaline soil than in the neutral and acidic soils. Median lethal concentration of fenamiphos in the neutral soil was 228 mg kg(-1) soil. Residues of fenamiphos caused a significant reduction in the biomass of worms, especially the ones exposed to the pesticide in the acidic soil. In vitro experiments suggested that fenamiphos was biotransformed in the earthworms principally to its oxide metabolite. To our knowledge, this is the first study demonstrating the biotransformation of fenamiphos by E. fetida.

Fenamiphos and related organophosphorus pesticides: environmental fate and toxicology.

In this review, we emphasize recent research on the fate, transport, and metabolism of tree selected organophosphorus pesticides (fenamiphos, isofenphos, and coumaphos) in soil an water environments. This review is also concerned with the side effects of these pesticides on nontarget organisms. Despite the fact that fenamiphos is not very mobile, its oxides have been detected in the groundwaters of Western Australia. Most organophosphorus pesticides generally are chemically unstable and underfo microbial degradation in soil and water environments. Enhanced biodegradation of many organophosphorus pesticides upon their repeted applications to soil and water is well established. Myriads of soil microorganisms, bacteria in particular, exhibit an exceptional capacity to transform many organophosphorus pesticides. Fenamiphos can undergo rapid microbially mediated degradation via oxidation to its oxides (sulfoxide and sulfone) and eventually to CO2 and water in soils, or via hydrolysis, in cultures of the soil bacterium, Brevinbacterium sp. There is evidence for enhanced biodegradation of (i) isofenphos in soils with a long history of use and (ii) coumaphos in cattle dip by bacterial cultures to chlorferon and diethylthiophosphoric acid.

Hydrolysis of fenamiphos and its toxic oxidation products by Microbacterium sp. in pure culture and groundwater.

A bacterium with an exceptional ability to hydrolyse fenamiphos and its toxic oxidation products fenamiphos sulfoxide and fenamiphos sulfone, all possessing POC bond was isolated from soil. Based on 16S rRNA gene determination, this bacterium was putatively identified as Microbacterium esteraromaticum. The phenols (fenamiphos phenol, sulfoxide phenol and sulfone phenol) formed during bacterial hydrolysis resisted further degradation in mineral salts medium and sterile groundwater, but were transitory in non-sterile groundwater due to the catabolism of native microorganisms. Also, the cell-free preparation of this bacterium was highly effective in hydrolysing fenamiphos and its oxides. These results demonstrate the potential of this bacterium to detoxify pesticide waste in the environment including the groundwater.

Effect of insecticide fenamiphos on soil microbial activities in Australian and Ecuadorean soils.

The effect of fenamiphos, a widely used organophosphorus pesticide, on important soil microbial activities such as dehydrogenase, urease and potential nitrification in four soils from Australia and Ecuador were studied. The results showed fenamiphos in general was not toxic to dehydrogenase and urease up to 100 mg/Kg soil. However potential nitrification was found to be highly sensitive to fenamiphos with a significant inhibition recorded even at 10 mg/Kg soil. In general, the nitrification activity in soils was decreased with an increase in fenamiphos concentration. The calculated EC(50) values for nitrification in all the tested soils ranged between 19 and 56 mg fenamiphos/kg dry soil. This study suggests that fenamiphos is likely to be detrimental to nitrification at field application rates.

Biodegradation of the pesticide fenamiphos by ten different species of green algae and cyanobacteria.

The degradation of an organophosphorus pesticide, fenamiphos, by different species of five green algae and five cyanobacteria was studied. All the species tested were able to transform fenamiphos to its primary oxidation product, fenamiphos sulfoxide (FSO), while the majority of these cultures were able to hydrolyze FSO to fenamiphos sulfoxide phenol (FSOP). Fenamiphos sulfone phenol, FSOP, and FSO were detected in the culture extracts of these algae and cyanobacteria. This is the first report on the biodegradation of a toxic pesticide, fenamiphos, by cyanobacteria. The ability of these algae and cyanobacteria to detoxify fenamiphos can be gainfully used in bioremediation of this pesticide and its toxic metabolites.

Sorption of fenamiphos to different soils: the influence of soil properties.

Fenamiphos (0-ethyl-0(3-methyl-4-methylthiophenyl)-isopropylamido-phosphate) is a widely used nematicide and insecticide in bowling greens and agriculture, but information on its sorption including its metabolites is limited. Hence, the sorption of fenamiphos (nematicide) and its major degradation products fenamiphos sulfoxide (FSO) and fenamiphos sulfone (FSO2) were determined in thirteen contrasting soils collected from Australia and Ecuador. The sorption coefficients (Kd) exhibited a wide range of variation from 2.48 to 14.94 L/Kg for fenamiphos; from 0 to 7.42 L/Kg for FSO and from 0 to 9.49 L/Kg for FSO2. The sorption affinity of the three compounds for all soils tested was as follows: fenamiphos > fenamiphos sulfone > fenamiphos sulfoxide. The results showed that the sorption of fenamiphos and its metabolites in some soils is very low, and in one case is nonexistant for the metabolites. This is of particular concern as due to its low sorption coefficient, the compound could easily migrate and contaminate water bodies. Fenamiphos and its oxidation products have been reported to be highly toxic to aquatic invertebrates and therefore, the information generated in this study assumes great importance in the risk assessment of fenamiphos and its metabolites in the environment.

Toxicity and transformation of fenamiphos and its metabolites by two micro algae Pseudokirchneriella subcapitata and Chlorococcum sp.

The acute toxicity of an organophosphorous pesticide, fenamiphos and its metabolites, fenamiphos sulfoxide (FSO), fenamiphos sulfone (FSO(2)), fenamiphos phenol (FP), fenamiphos sulfoxide phenol (FSOP) and fenamiphos sulfone phenol (FSO(2)P), to the aquatic alga Pseudokirchneriella subcapitata and the terrestrial alga Chlorococcum sp. was studied. The toxicity followed the order: fenamiphos phenol>fenamiphos sulfone phenol>fenamiphos sulfoxide phenol>fenamiphos. The oxidation products of fenamiphos, FSO and FSO(2) were not toxic to the algal species up to 100 mg L(-1). Both algae were able to transform fenamiphos, FSO and FSO(2), while the phenols were found to be stable in the incubation media. Bioaccumulation of both fenamiphos and its metabolites was observed in the case of Chlorococcum sp. while only metabolites were accumulated in P. subcapitata. This study demonstrates that (i) the hydrolysis products of fenamiphos, FSOP and FSO(2)P are more toxic to both fresh water and soil algae than their parent chemicals, (ii) further fenamiphos can be transformed and bioconcentrated by these algae. Therefore, contamination of natural environments such as waterbodies with fenamiphos or its metabolites can have adverse impacts on the food chain and associated biota (especially to the primary consumers such as Daphnia) since algae are the primary producers located at the base of the food chain. Further, the finding that the fenamiphos phenols are more toxic to algae highlights the need to consider the transformation products in ecological risk assessment of fenamiphos.

Degradation of fenamiphos in soils collected from different geographical regions: the influence of soil properties and climatic conditions.

The persistence of fenamiphos (nematicide) in five soils collected from different geographical regions such as Australia, Ecuador and India under three temperature regimes (18, 25 and 37 degrees C) simulating typical environmental conditions was studied. The effect of soil properties (soil pH, temperature and microbial biomass) on the degradation of fenamiphos was determined. The rate of degradation increased with increase in temperature. Fenamiphos degradation was higher at 37 degrees C than at 25 and 18 degrees C (except under alkaline pH). The degradation pathway differed in different soils. Fenamiphos sulfoxide (FSO) was identified as the major degradation product in all the soils. Fenamiphos sulfone (FSO2), and the corresponding phenols: fenamiphos phenol (FP), fenamiphos sulfoxide phenol (FSOP) and fenamiphos sulfone phenol (FSO2P) were also detected. The degradation of fenamiphos was faster in the alkaline soils, followed by neutral and acidic soils. Under sterile conditions, the dissipation of the pesticide was slower than in the non-sterile soils suggesting microbial role in the pesticide degradation. The generation of new knowledge on fenamiphos degradation patterns under different environmental conditions is important to achieve better pesticide risk management.

Toxicity of chlorpyrifos and TCP alone and in combination to Daphnia carinata: the influence of microbial degradation in natural water.

The acute toxicity of chlorpyrifos and its principal metabolite 3,5,6-trichloropyridinol (TCP) alone and in combination to a cladoceran, Daphnia carinata, was studied in both cladoceran culture medium and natural water collected from a local suburban stream. TCP was found to be more toxic than its parent chemical chlorpyrifos to Daphnia survival in cladoceran culture medium. However, TCP in natural water was not toxic to D. carinata up to 2 microgL(-1). The LC(50) values for chlorpyrifos, TCP and chlorpyrifos+TCP were 0.24, 0.20 and 0.08 microgL(-1), respectively, in cladoceran culture medium. Although the parent chemicals and their degradation products co-exist in natural waters, the existing guidelines for water quality are based on individual chemicals. The results of this investigation suggest that chlorpyrifos and TCP can interact synergistically, additively or antagonistically, resulting in an increase or decrease in the overall toxicity of the mixture compared to individual compounds. The indigenous microorganisms in natural water could play a significant role in degradation of these compounds thereby influencing their toxicity in receiving waters. This study clearly suggests that the joint action of pesticides and their degradation products should be considered in the development of water quality guidelines. To our knowledge, this is the first study on the interactive effect of chlorpyrifos and TCP to a cladoceran and suggests that these two compounds are non-toxic when present together at concentrations up to 0.12 microgL(-1). However, these compounds together act additively at and above 0.5 microgL(-1) to fresh water invertebrates and therefore pollution with these compounds may adversely affect natural ecosystems.

Toxicity of fenamiphos and its metabolites to the cladoceran Daphnia carinata: the influence of microbial degradation in natural waters.

The acute toxicity of an organophosphorous pesticide, fenamiphos and its metabolites, fenamiphos sulfoxide, fenamiphos sulfone, fenamiphos phenol, fenamiphos sulfoxide phenol and fenamiphos sulfone phenol, to a cladoceran, Daphnia carinata was studied in both cladoceran culture medium and natural water collected from a local river. The toxicity followed the order: fenamiphos>fenamiphos sulfone>fenamiphos sulfoxide. The hydrolysis products of fenamiphos, F. sulfoxide (FSO) and F. sulfone (FSO(2)) (F. phenol, FSO phenol and FSO(2) phenol) were not toxic to D. carinata up to 500microgl(-1) water, suggesting hydrolysis reaction leads to detoxification. Also the toxicity was reduced in natural water compared to the cladoceran culture medium due to microbial mediated degradation of toxicants in the natural water. Fenamiphos and its metabolites were stable in both cladoceran water and filter-sterilised natural water while these compounds showed degradation in unfiltered natural water implicating the microbial role in degradation of these compounds. To our knowledge this is the first study on acute toxicity of fenamiphos metabolites to cladoceran and this study suggests that the organophosphate pesticides are highly toxic to fresh water invertebrates and therefore pollution with these compounds may adversely affect the natural ecosystems.