The role of toxicology in the evaluation of new agrochemicals

Abstract

The use of agrochemicals like crop protecting agents, veterinary disinfectants, and wood preservatives may result in (un)intentional exposure of the environment, animals and man. This paper deals with current testing strategies to assess the potential health risks for humans exposed to these chemicals during production or application or via consumption of foods containing pesticide residues.

Principles and procedures for safety assessment of pesticide residues in food as developed by WHO/FAO are described. Different types of toxicity studies in mammalian test animal species are discussed and a strategy is outlined in order to characterize the toxicity profile of a compound and the relationship between applied doses and adverse effects. Safety testing of agrochemicals should be carried out in relation to its intended use, and in particular attention will be paid to toxicity testing of residues of pesticides in food. Extrapolation of results from animal studies to humans and the use of safety factors is discussed.

Besides the use of animal protocol studies for safety testing of agrochemicals, the potential use of in‐vitro models derived from organs and tissues of animals is discussed. Data on the in‐vitro metabolism of thiabendazole, aldicarb and alachlor are discussed in order to demonstrate that such data may complement or partly substitute whole animal experimentation.

Principles and procedures for safety testing of residues of agrochemicals in food as applied during the last three decades, constitute a ‘safety‐first’ approach, providing sufficient safety margins for the consumer of foods which may contain low levels of residues of agrochemicals.     

Mercury transfer from fish carcasses to scavengers in boreal lakes: the use of stable isotopes of mercury

Scavengers play an important role in the flow of energy, matter and pollutants through food webs. For methylmercury (MeHg), which biomagnifies along food chains, the movement of this metal from fish carcasses to aquatic scavengers has never been demonstrated. We measured the transfer of MeHg from fish carcasses to scavenging leeches in two lakes and in the laboratory. The results of a field experiment indicated that leeches were attracted to fish carcasses and that their Hg concentrations increased by as much as a factor of 5 during the time that Hg-rich fish were available for consumption. Under controlled conditions, we exposed leeches to (202)Hg-labelled fish that had been marked in situ following a whole lake (202)Hg addition. Leeches rapidly accumulated Hg from carcasses, and within two weeks assumed the isotopic signature of the carcasses. Necrophagous invertebrates could therefore return Hg from fish carcasses to other trophic levels in lakes.     

Diclofenac disposition in Indian cow and goat with reference to Gyps vulture population declines

Gyps vultures across India are declining rapidly and the NSAID diclofenac has been shown to be the major cause. Vultures scavenge livestock carcasses that have been treated with diclofenac within the days preceding death. We present data on diclofenac disposition in Indian cow and goat, and field data on the prevalence of diclofenac in carcases in the environment. In the disposition experiment, animals were treated with a single intramuscular injection of diclofenac at 1000 microg kg-1 bw. In cow, diclofenac was detectable in liver, kidney and intestine up to 71 h post-treatment; in plasma, half-life was 12.2 h. In goat, tissue residues were undetectable after 26 h. Prevalence of diclofenac in liver from 36 dead livestock collected in the field was 13.9%. Data suggest that diclofenac residues in Indian cow and goat are short-lived, but diclofenac prevalence in carcasses available to vultures may still be very high.     

Pesticide residues in freshwater and marine zooplankton: a review

A review of the scientific literature on pesticide residues in freshwater and marine zooplankton indicates that despite the great number of pesticides in current use, only residues of the persistent organochlorine insecticides, many of which have been restricted or removed from general use in North America, have been determined. Much of this information is outdated. In addition, with the exception of the Great Lakes on which limited information is available, reports on residues in freshwater zooplankton are rare. Information on residues of the newer, less persistent but heavily used pesticides is lacking. As an alternative to field sampling and chemical analysis of endemic populations of zooplankton, scientists have modeled the bioaccumulation of pesticides in zooplankton using either laboratory microcosms or mathematical equations. However, the extent and importance of trophic transfer to higher food levels through this intermediary group of organisms is still controversial. In addition, the relationship between accumulation of pesticides and toxicity to zooplankton remains unresolved.     

The relationship between dermal pesticide exposure by fruit harvesters and dislodgeable foliar residues

Dermal pesticide exposure rates, expressed in mg/hr, by strawberry and blueberry harvesters and dislodgeable foliar pesticide residues were determined in 7 separate field experiments during 1981-1983 in California and Oregon. The pesticides which were studied included captan, vinclozolin, carbaryl, and methiocarb. A positive correlation between these two parameters was found and compared with literature values involving different pesticides and tree crops. The ratio between dermal exposure rate and dislodgeable foliar residues, the units of which are area/time, may have a possible use as an empirical factor for a first approximation of dermal exposure rates by fruit harvesters without the involvement of human subjects.     

常温条件下CAST工艺亚硝酸型硝化的实现及特性

采用循环式活性污泥法(CAST)处理模拟生活污水,通过控制曝气量,使反应器中DO在0.13～0.74 mg/L之间,在常温下快速实现亚硝酸型硝化,然后增大曝气量使反应器内DO在0.7～3.36 mg/L之间,控制曝气时间1.5 h,考察系统内亚硝酸型硝化的维持情况。结果表明,14℃条件下,通过先控制低溶解氧浓度再控制曝...     

1H-NMR-based profiling of organic components in leachate from animal carcasses disposal site with time

Leachate, generated by the decomposition of animal carcasses, presents many environmental, sanitary, and food safety hazards. However, research on the characteristics of leachate is lacking. In this study, we performed biochemical profiling of leachate from two animal species (pig and cattle) in two soil types (sandy loam and sandy soil) using ¹H-NMR-based profiling, followed by multivariate data analysis. The leachate was collected from a well-controlled artificial burial site over a 31-week period. Principal components analysis (PCA) of the NMR data showed similar patterns between species and soil types. Organic components, including organic acids and phenols, predominated, and their levels increased with time. The methylamine level in leachate from pig carcasses 18 weeks following burial was significantly higher than that from cattle carcasses; leachate from cattle carcasses in sandy soil 1 week after burial contained unique components (specifically ethanol, formate, alanine, N-methylation, and taurine), in contrast with those from sandy loam soil. This study suggests that a NMR-based profiling approach is useful to characterize the organic components in leachate from animal carcasses over time.     

Effect of bound residues of metsulfuron-methyl in soil on rice growth

A pot experiment was conducted to appraise the hazards of bound residues of metsulfuron-methyl in soil at six levels (0, 0.050, 0.089, 0.158, 0.281, and 0.500 mg kg(-1)) to the growth of four rice varieties (Xiushui 63, Eryou 810, Liangyoupeijiu, and Zhenong 952). The morphological characteristics of rice roots like root number, total length, surface area of rice roots, and rice biomass were determined. The results showed that the bound residues of metsulfuron-methyl in soil impacted the growth of rice. Root number, total length of roots, surface area of roots, and biomass were restrained by bound residues of metsulfuron-methyl in soil. The inhibition rate of root growth increased from 69.46-81.32% to 85.18-95.97% with the increasing of levels of bound residues of metsulfuron-methyl from 0.05 mg kg(-1) to 0.50 mg kg(-1). The number of rice roots could be taken as a sensitive index to screen the rice varieties endurable to bound residues of metsulfuron-methyl in soil and to predict the potential hazards of bound residues of metsulfuron-methyl in soil to rice. The level of bound residues of metsulfuron-methyl in soil causing the root numbers decreased by 50% (IC50) followed the order of Xiushui 63 < Eryou 810 < Liangyoupeijiu < Zhenong 952.     

Radionuclides and the birds at Ravenglass

Since 1983, concern has been expressed about the apparent decline in numbers of birds in the Ravenglass estuary in west Cumbria, particularly of the black-headed gull colony on the Drigg dunes, and suggestions have been made that this decline might be due to excessive radiation in the birds' food and their general environment. Twelve species of marine invertebrates from Ravenglass, most of them known to be important foods for birds, were analysed, and further samples were taken from sites along the west Cumbrian coast. None of these samples showed excessive contamination with any of the radionuclides analysed. Analysis of a sample of bird carcasses from the areas showed oystercatchers (Haematopus ostralegus) and shelduck (Tadorna tadorna) to have some of the highest concentrations of (137)Cs in their tissues; yet their breeding success and populations were not affected. Black-headed gulls, on the other hand, were found to be feeding mainly inland, and were the least contaminated with radionuclides of all the birds at Ravenglass, yet this species and its breeding success were in decline. Calculations of the total dose equivalent rate to the whole body of the most contaminated black-headed gull amounted to 9.8 x 10(-4) mSvh(-1) (approximately equal to 8.4 x 10(-4) mGy h(-1), whole body absorbed dose rate), and the background exposure dose was of the order of 8.3 x 10(-4) mGy h(-1). As a minimum chronic dose of 1000 mGy day(-1) has been found necessary to retard growth of nestling birds, and 9600 mGy over 20 days of incubation to cause the death of 50% of embryos in black-headed gulls' eggs, the concentrations of radionuclides in the foods, body tissues and general environment were at least three orders of magnitude too low to have had any effect. The more likely cause of the desertion of the gullery was the combination of an uncontrolled fox population, the severest outbreak of myxomatosis amongst the rabbits since 1954 and the driest May-July period on record, all in the same year (1984).     

PCDD/F levels in plasma of a belgian population before and after the 1999 belgian PCB/DIOXIN incident

We evaluated the impact of the 1999 Belgian dioxin incident on the blood plasma polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) levels among 232 Belgian blood donors (74% men, mean age 47 years). The Red Cross made plasma samples from before the incident of these donors available. A second plasma sample was collected during the second half of 2000. The sum of the 17 PCDD/F congeners was significantly lower in 2000 compared to 1998 (417 pg/g fat versus 445 pg/g fat, respectively). This could be completely attributed to the significant decrease of OctaCDD (301 pg/g fat in 2000 versus 277 pg/g fat in 1998). Moreover a slight but significant decrease was observed for 2,3,7,8-TetraCDF and for 1,2,3,4,6,7,8-HeptaCDF. 1,2,3,7,8-PentaCDF and 2,3,4,7,8-PentaCDF however showed a slight but significant increase (respective levels in 1998 were 0.004 and 14.5 pg/g fat compared to 0.006 and 17.9 pg/g fat in 2000). Given their significantly higher presence in incident related food samples this increase can be attributed to the food contamination episode. However, the total toxicity remained unchanged (22.9 in 1998 versus 23.1 pg WHO-TEQ/g fat, p>0.05). Moreover the observed congener profiles and the total PCDD/F levels were similar to those of other European non-occupationally exposed populations. In conclusion, the 1999 PCB/dioxin incident was traceable in the plasma profiles (rise of the two specific PCDF congeners), but comparison of the results for both years indicates that the changes were too small to cause an adverse public health effect.     

Dietary mercury exposure and bioaccumulation in amphibian larvae inhabiting Carolina bay wetlands

Inorganic mercury and methylmercury concentrations were measured both in guts and remaining carcasses of southern leopard frog (Rana sphenocephala) larvae from 10 Carolina bay wetlands in South Carolina, USA. Significant variation among bays in methylmercury and inorganic mercury concentrations existed both in guts and carcasses. There was a moderate negative correlation between dissolved organic carbon concentration in bays and mean inorganic mercury concentrations in guts. There was also a weak positive correlation between pH in bays and mean methylmercury concentrations in carcasses. The ratio of methylmercury to inorganic mercury decreased with increasing total mercury concentration in guts and in larvae, but the rate of decrease was highly variable among bays. Ratios of concentrations in carcasses to concentrations in guts were inversely related to gut concentration. Mercury concentrations in carcasses in some bays were within the range of concentrations at which adverse effects have been observed in laboratory studies of R. sphenocephala.     

Characterization of food waste from different sources in Hong Kong

Food waste from different sources or at different generation stages may have different compositional characteristics and is therefore suitable for recycling into different products. To have a better understanding of their chemical composition, five food waste types were collected, namely, household kitchen waste (HH), preconsumption and postconsumption food waste from a hotel (Hpr and Hpo), wet market food waste (WM) and kitchen waste from a Chinese restaurant (CR), and their compositions were assessed monthly for 1 year. They served as suitable feedstock for various conversion technologies according to their chemical profiles. HH and CR had higher crude protein content (26%) and considerable amounts of minerals, making them nutritionally suitable for feeding animals. Preconsumption food wastes Hpr and WM had more favorable C:N ratios (16.5–17.4) and crude fat contents (4.6–6.5%) as feedstock for composting. Postconsumption food wastes were potential feedstock for the production of biogas and biodiesel because of the higher dry matter (>26%) and fat content (>13%). The coefficients of variation (CV) in all nutrients analyzed except Ca for postconsumption food wastes ranged from 5% to 37%, which showed lower temporal variability than preconsumption food wastes (CVs 10–131%). This implies that the composition of postconsumption food waste was relatively less fluctuating and can be considered a more reliable feedstock for food waste conversion.

Implications: Characterization of food waste composition from different sources and determination of their temporal variation were performed to understand their characteristics and facilitate sound food waste management. Separating food wastes according to their sources and types helps reduce their composition variability, and thus increases the consistence in food-waste-derived products and recycling success. Study on temporal variation indicates that postconsumption food wastes varied less with time and could serve as reliable feedstocks for food waste conversion.     

Modelling the effect of acidity on mercury uptake by walleye in acidic and circumneutral lakes

An association between acidification of lakes and high mercury concentrations in fishes has been reported. In northern Wisconsin (USA), for example, walleye (Stizostedion vitreum) in naturally acidic lakes have higher mercury concentrations than walleye in circumneutral lakes (Weiner, 1983). In this study a bioenergetic based model for mercury uptake is applied to identify potential causes of higher mercury concentrations in fishes living in acidic lakes. Application of the model to walleye populations in northern Wisconsin indicates that higher mercury concentrations in acidic lakes are most likely a result of both increased concentrations in the water and increased efficiencies of uptake from water. Higher concentrations in the water would result in higher concentrations in the food.     

Microalgae biosynthesis of silver nanoparticles for application in the control of agricultural pathogens

The occurrence of diseases in cultivars has caused significant losses in global food production. The advancement of nanobiotechnology makes it possible to obtain new products to be used in the control of pathogens in cultivars. Silver nanoparticles can be synthesized by microalgae and are widely known for their antimicrobial activity. In addition, the biomass produced in microalgal culture for the biosynthesis of the nanoparticles also demonstrates antimicrobial properties, as it can increase the antibacterial and antifungal potential of the silver nanoparticles. In this context, this article addresses the use of microalgae to biosynthesize silver nanoparticles simultaneously with biomass production. In addition, we demonstrate the antimicrobial potential of these nanomaterials, as well as of the microalgal biomass produced in biosynthesis, to use in the control of pathogens in agriculture.     

Dietary intake of PCDD/F by small children with different food consumption measured by the duplicate method

The dietary intake of PCDD/F by 42 small children, 21 boys and 21 girls in the age range 14-47 months, with different food consumption behaviour living in urban and rural areas of Germany was measured by the duplicate method with a 7 day sampling period from May to September 1998. The PCDD/F-levels in the food duplicates were in the range 39.2-325 fg I-TEq/g(dry weight) (median: 90.7; arithmetic mean: 96.6) and the doses were in the range 0.681-5.43 with a median of 1.56 and an arithmetic mean (AM) of 1.60 pg I-TEq/(kg(body weight) x d). Children living in an urban industrialized area with food consumption including products from the family owned vegetable gardens or the surrounding area and/or products from domestic animals showed no statistically significant different concentrations in the food duplicates or in the dietary intake of PCDD/F, calculated as I-TEq, than children living in a rural area with similar food consumption behavior or than children consuming exclusively food from the supermarket.     

Chemical trends in Finnish wildlife: A study on time trends in starlings during 1967–1983

The OECD monitoring programmes 1966–1971 and 1972–1975 have been extended at national level in Finland to 1983 by analysing chlorinated hydrocarbons, mercury and chlorophenols in starlings (terrestrial environment). At the end of the study period levels in fresh muscles were for DDE 10, PCB 30, HCB 1, Lindan 8 and mercury 50 ppb. Of chlordane residues only traces of oxychlordane were found. Ten different chlorophenol compounds were detected at ppb levels, but most of them in only few samples. Pentachlorophenol was most frequently found. Statistical treatment of the analysis results gave some decreasing trends which were very significant for DDE, DDT and PCB 1967–1983, significant for mercury 1967–1983 and somewhat significant for lindane 1978–1983.     

Halogenated diphenyl ethers identified in avian tissues and eggs by GC/MS

Chlorinated and brominated diphenyl ether compounds (DPEs) have been detected by gas Chromatography/ mass spectrometry (GC/MS) in eggs and carcasses of fish-eating birds from Louisiana, Michigan, Ohio, Rhode Island, Texas, Virginia, and Ontario, Canada. Three of these compounds were quantified; the highest concentration of 0.90 ppm tetrachloro DPE was found in a common tern carcass ( ) from Rhode Island. This is the first time that the halogenated DPEs have been reported in avian tissues. The significance of these residues is unknown.     

Organochlorine compounds in bovine milk from the state of Mato Grosso do Sul – Brazil

Organochlorines are highly hydrophobic, synthetic organic pollutants that accumulate in the environment and in food webs. The primary route of human exposure to organochlorines is through food-mainly fat-rich food of animal origin such as meat, fish, and dairy products. Here we determined the presence and concentration of organochlorine residues in pasteurized milk from Mato Grosso do Sul, Brazil, to monitor consumer exposure to these contaminants. Organochlorine pesticides in milk samples were analyzed using solid phase extraction in octadecyl silica-prepacked columns and identified by gas chromatography using an electron capture detector. Of the 100 composite samples analyzed, more than 90% contained residues of organochlorine pesticides: aldrin was present in 44% of the samples, followed by ∑DDT (36%), mirex (34%), endosulfan (32%), chlordane (17%), dicofol (14%), heptachlor (11%) and dieldrin (11%). Compared to the values established by law, the concentration of the compounds in some samples was above the reference values. Given the importance that milk and its products have in the human diet, it is essential to know whether the levels of pesticide residues are kept well below the recommended levels to minimize the risk to human health.     

A systematic review and meta-analysis of the impacts of glyphosate on the reproductive hormones

Environmental Science and Pollution Research - Worldwide use of glyphosate is constantly increasing and its residues are detected in drinking water, agriculture, and food products. There are...     

Occurrence, source diagnosis, and biological effect assessment of DDT and its metabolites in various environmental compartments of the Pearl River Delta, South China: A review

This review summarizes and analyzes available data in the literature (mostly after 2000) on the occurrence of dichlorodiphenyltrichloroethane (DDT) and its main metabolites, dichlorodiphenyldichloroethane (DDD) and chlorodiphenyldichloroethylene (DDE), in the environment of the Pearl River Delta (PRD), South China. Generally, the concentration levels of the sum of DDT, DDD, and DDE, designated as DDTs thereafter, have not significantly declined since 1983. However, the composition of DDTs residues has changed with time. DDTs in soil, freshwater sediment and freshwater fish species were mainly residues from chronological use. There is evidence that new point sources, such as dicofol and anti-fouling paint, may have contributed DDTs to various environmental compartments. Risk assessment against existing criteria indicated that the levels of DDTs in water and some fish species may pose adverse effects to humans or wildlife, and those in sediment/soil may also cause negative impacts to the eco-environment of the PRD.