Kristine A. Krogh

Environmental properties and effects of nonionic surfactant adjuvants in pesticides: a review

Little is known about the environmental fate of adjuvants after application on the agricultural land. Adjuvants constitute a broad range of substances, of which solvents and surfactants are the major types. Nonionic surfactants such as alcohol ethoxylates (AEOs) and alkylamine ethoxylates (ANEOs) are typically examples of pesticide adjuvants. In view of their chemical structure this paper outlines present knowledge on occurrence, fate and effect on the aquatic and terrestrial environment of the two adjuvants: AEOs and ANEOs. Both AEOs and ANEOs are used as technical mixtures. This implies that they are not one single compound but a whole range of compounds present in different ratios. Structurally both groups of substances have a mutual core with side chains of varying lengths. Each of these compounds besides having the overall ability to distribute between different phases also possesses some single compound behaviour. This is reflected in the parameters describing the fate e.g. distribution coefficient, leaching, run-off, adsorption to soil, degradation and effects of these substances. The adsorption behaviour of ANEOs in contrast to AEOs is particularly variable and matrix dependent due to the ability of the compound to ionise at environmentally relevant pH. Probably because the compounds exceeds high soil adsorption and are easily degradable which is reflected in the low environmental concentrations generally found in monitoring studies. The compounds generally possess low potency to both terrestrial and aquatic organisms. The major environmental problem related to these compounds is the ability to enhance the mobility of other pollutants in the soil column.

Development of an analytical method to determine avermectins in water, sediments and soils using liquid chromatography–tandem mass spectrometry

A comprehensive analytical multi-residue method has been developed for the determination of seven avermectins (abamectin, doramectin, ivermectin, emamectin benzoate, eprinomectin, moxidectin and selamectin) in surface water, sediment and soil samples. Solid samples were extracted applying pressurised liquid extraction followed by a solid-phase extraction (SPE) clean-up step. For aqueous samples, extraction was done utilising only SPE. All compounds were measured using liquid chromatography coupled to tandem mass spectrometry using atmospheric pressure chemical ionisation. The recoveries were 38-67% (relative standard deviation: 9-26%), 63-88% (16-23%) and 63-80% (9-15%) for spiked Rhine water, spiked sediment and spiked soil samples, respectively, and limit of quantifications were 2.5-14 ngl(-1) in water and 0.5-2.5 ngg(-1) in soil and sediment.

Environmental risk assessment of ivermectin: A case study.

The veterinary parasiticide ivermectin was selected as a case study compound within the project ERAPharm (Environmental Risk Assessment of Pharmaceuticals). Based on experimental data generated within ERAPharm and additional literature data, an environmental risk assessment (ERA) was performed mainly according to international and European guidelines. For the environmental compartments surface water, sediment, and dung, a risk was indicated at all levels of the tiered assessment approach. Only for soil was no risk indicated after the lower tier assessment. However, the use of effects data from additional 2-species and multispecies studies resulted in a risk indication for collembolans. Although previously performed ERAs for ivermectin revealed no concern for the aquatic compartment, and transient effects on dung-insect populations were not considered as relevant, the present ERA clearly demonstrates unacceptable risks for all investigated environmental compartments and hence suggests the necessity of reassessing ivermectin-containing products. Based on this case study, several gaps in the existing guidelines for ERA of pharmaceuticals were shown and improvements have been suggested. The action limit at the start of the ERA, for example, is not protective for substances such as ivermectin when used on intensively reared animals. Furthermore, initial predicted environmental concentrations (PECs) of ivermectin in soil were estimated to be lower than refined PECs, indicating that the currently used tiered approach for exposure assessment is not appropriate for substances with potential for accumulation in soil. In addition, guidance is lacking for the assessment of effects at higher tiers of the ERA, e.g., for field studies or a tiered effects assessment in the dung compartment.

Liquid chromatography–mass spectrometry method to determine alcohol ethoxylates and alkylamine ethoxylates in soil interstitial water, ground water and surface water samples

Alcohol ethoxylates (AEs) and alkylamine ethoxylates (AMEs) are used as adjuvants in pesticide formulations. Analytical procedures for these compounds in environmental aqueous samples using LC-MS are presented. Sample preparation uses solid-phase extraction with Porapak Rdx cartridges. Detection limits and recoveries in ground water and surface water are, respectively, AEs: 16-60 ng/l, 35-93% and AMEs: 0.3-6 microg/l, 28-96%. The lower recoveries are obtained for the apolar surfactants. The procedure was employed on samples of ground water and soil interstitial water collected from farming areas. The individual AEs were detected at concentration levels ranging from 33 to 189 ng/l water.

Fate and antibacterial potency of anticoccidial drugs and their main abiotic degradation products.

The antibacterial potency of eight anticoccidial drugs was tested in a soil bacteria bioassay (pour plate method), EC(50)-values between 2.4 and 19.6 microM were obtained; however, one compound, nicarbazin exhibited an EC(50)-value above the maximum tested concentration (21 microM, 9.1 mg L(-1)). The potency of mixtures of two of the compounds, narasin and nicarbazin, was synergistic (more than additive) with 10-fold greater antibacterial potency of the mixture than can be explained by their individual EC(50)-values. The influence of pH, temperature, oxygen concentration and light on the transformation of robenidine and salinomycin was investigated. Robenidine was transformed by photolysis (DT(50) of 4.1 days) and was unstable at low pH (DT(50) of approximately 4 days); salinomycin was merely transformed at low pH, the latter into an unknown number of products. The antibacterial potency of the mixtures of transformation products of robenidine after photolysis and at low pH was comparable with that of the parent compound. Finally five photo-transformation products of robenidine were structural elucidated by accurate mass measurements, i-FIT values (isotopic pattern fit) and MS/MS fragmentation patterns.

Analysis of the dissipation kinetics of ivermectin at different temperatures and in four different soils

The study target was to assess the usefulness of the OECD test guideline 307 for the veterinary pharmaceutical ivermectin. Laboratory microcosm studies were conducted to investigate the aerobic and anaerobic transformation of ivermectin in soils from three locations in Europe (York, Madrid and Tåstrup) and an artificial soil. The reason to include an artificial soil in the study was to understand the exposure potential of ivermectin in a parallel eco-toxicological study with non-target organisms in this soil for a longer duration. Three kinetic models (first-order (SFO), availability-adjusted first-order (AAFO) and bi-exponential first-order (BFO)) were applied to fit the observed transformation dynamics and to derive dissipation times. Dissipation rates were highly dependent on the tested soils. Under aerobic conditions, dissipation was remarkably faster in the three natural soils tested (DT(50)=16.1-36.1d) than in the artificial soil (DT(50)>500d). Furthermore, a clear increase in DT(50) values was seen when the temperature was lowered from 20 to 6 degrees C. The results indicated that dissipation in soils with comparably strong sorption and low degrees of desorption (i.e. the York soil and to some extent the Tåstrup soil) were best described by the AAFO model. While dissipation in the Madrid soil which had a lower sorption coefficient and a higher degree of reversibility of sorption could be satisfactorily described with the SFO model. Our data further showed that no significant dissipation occurred under anaerobic conditions.

Determination of ivermectin and transformation products in environmental waters using hollow fibre-supported liquid membrane extraction and liquid chromatography-mass spectrometry/mass spectrometry

A simple and easy-to-use extraction method for aqueous samples based on hollow fibre-supported liquid membrane (HF-SLM) followed by liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) was developed to determine ivermectin and transformation products, the monosaccharide (TP1) and the aglycon of ivermectin (TP2). The proposed method attained enrichment factors up to 80, after optimising parameters, such as fibre length, organic solvent, stirring speed, salt level, pH in samples/fibre, extraction time and fibre emptying technique. Method validation with tap and lake water samples provided good linearity and detection limits of 0.2, 1.6 and 0.9 microg/l for ivermectin, TP1 and TP2 in lake water with RSD below 15%.

Determination of ten steroid hormones in animal waste manure and agricultural soil using inverse and integrated clean-up pressurized liquid extraction and gas chromatography-tandem mass spectrometry

This paper presents a novel analytical methodology for the simultaneous determination of nine native and one synthetic steroid hormone in animal manure and agricultural soil. The optimized method applies pressurized liquid extraction (PLE) on manure samples packed in a 22 mL PLE cell: firstly by flushing the sample with heptane to remove unwanted matrix components (inverse-PLE, i-PLE) and secondly, performing internal clean-up (ic-PLE) and eluting the steroid hormones by attaching an additional 11 mL PLE cell downstream packed with graphite, silica and alumina. The PLE extracts were further cleaned by a two step solid phase clean-up (aminopropyl and silica gel), and in combination with a one hour derivatization the samples could be analyzed utilizing a GC-MS/MS system with PTV injector. Cholesterol, sitosterol and coprostanols were added and monitored during method development experiments as surrogates for environmental interfering compounds. The optimization demonstrated that the surrogate interfering compounds could be fractionated from the steroid hormones during the i-PLE step. The absolute PLE recoveries for the steroid hormones were between 67 and 107% from 0.5 g manure spiked with 50 ng. The method was applied on several manure and agricultural soil samples, demonstrating high levels of steroid hormones in manure and amended soils.

Development of an analytical methodology for the determination of the antiparasitic drug toltrazuril and its two metabolites in surface water, soil and animal manure

This paper presents the development, optimization and validation of a LC-MS/MS methodology to determine the antiparasitic veterinary drug toltrazuril and its two main metabolites, toltrazuril sulfoxide and toltrazuril sulfone, in environmental surface water, soil and animal manure. Using solid phase extraction and selective pressurized liquid extraction with integrated clean-up, the analytical method allows for the determination of these compounds down to 0.06-0.13 ng L(-1) in water, 0.01-0.03 ng g(-1)dw in soil and 0.22-0.51 ng g(-1) dw in manure. The deuterated analog of toltrazuril was used as internal standard, and ensured method accuracy in the range 96-123% for water and 77-110% for soil samples. The developed method can also be applied to simultaneously determine steroid hormones in the solid samples. The antiparasitic drug and its metabolites were found in manure and soil up to 114 and 335 pg g(-1) dw, respectively. Little is known regarding the environmental fate and effects of these compounds; consequently more research is urgently needed.

Development and validation of an SPE methodology combined with LC-MS/MS for the determination of four ionophores in aqueous environmental matrices

A multi-residue analytical methodology has been established for the determination of the four ionophores: lasalocid, monensin, salinomycin and narasin in aqueous environmental matrices, using nigericin as internal standard. The samples were filtrated prior to solid phase extraction. All compounds were measured using liquid chromatography coupled to tandem mass spectrometry applying electro spray ionisation. The absolute recoveries ranged from 92 to 110% (relative standard deviation: 2–14%) for spiked river water. The final method allowed for detection of ionophores down to a few ng/L in natural water bodies with LOQs for the entire methodology being 40, 49, 67, and 14 ng/L for lasalocid, monensin, salinomycin, and narasin, respectively.