Distribution and chemical fate of ³6Cl-chlorine dioxide gas during the fumigation of tomatoes and cantaloupe.

The distribution and chemical fate of (36)Cl-ClO2 gas subsequent to fumigation of tomatoes or cantaloupe was investigated as were major factors that affect the formation of chloroxyanion byproducts. Approximately 22% of the generated (36)Cl-ClO2 was present on fumigated tomatoes after a 2 h exposure to approximately 5 mg of (36)Cl-ClO2. A water rinse removed 14% of the radiochlorine while tomato homogenate contained ∼63% of the tomato radioactivity; 24% of the radiochlorine was present in the tomato stem scar area. Radioactivity in tomato homogenate consisted of (36)Cl-chloride (≥80%), (36)Cl-chlorate (5 to 19%), and perchlorate (0.5 to 1.4%). In cantaloupe, 55% of the generated (36)Cl-ClO2 was present on melons fumigated with 100 mg of (36)Cl-ClO2 for a 2 h period. Edible cantaloupe flesh contained no detectable radioactive residue (LOQ = 0.3 to 0.4 µg/g); >99.9% of radioactivity associated with cantaloupe was on the inedible rind, with <0.1% associated with the seed bed. Rind radioactivity was present as (36)Cl-chloride (∼86%), chlorate (∼13%), and perchlorate (∼0.6%). Absent from tomatoes and cantaloupe were (36)Cl-chlorite residues. Follow-up studies have shown that chlorate and perchlorate formation can be completely eliminated by protecting fumigation chambers from light sources.

Ecotoxicology of synthetic pyrethroids.

In this chapter we review the ecotoxicology of the synthetic pyrethroids (SPs). SPs are potent, broad-spectrum insecticides. Their effects on a wide range of nontarget species have been broadly studied, and there is an extensive database available to evaluate their effects. SPs are highly toxic to fish and aquatic invertebrates in the laboratory, but effects in the field are mitigated by rapid dissipation and degradation. Due to their highly lipophilic nature, SPs partition extensively into sediments. Recent studies have shown that toxicity in sediment can be predicted on the basis of equilibrium partitioning, and whilst other factors can influence this, organic carbon content is a key determining variable. At present for SPs, there is no clear evidence for adverse population-relevant effects with an underlying endocrine mode of action. SPs have been studied intensively in aquatic field studies, and their effects under field conditions are mitigated from those measured in the laboratory by their rapid dissipation and degradation. Studies with a range of test systems have shown consistent aquatic field endpoints across a variety of geographies and trophic states. SPs are also highly toxic to bees and other nontarget arthropods in the laboratory. These effects are mitigated in the field through repellency and dissipation of residues, and recovery from any adverse effects tends to be rapid.

Probabilistic risk assessment of cotton pyrethroids: I. Distributional analyses of laboratory aquatic toxicity data.

This is the first in a series of five papers that assess the risk of the cotton pyrethroids in aquatic ecosystems in a series of steps ranging from the analysis of effects data through modeling exposures in the landscape. Pyrethroid insecticides used on cotton have the potential to contaminate aquatic systems. The objectives of this study were to develop probabilistic estimates of toxicity distributions, to compare these among the pyrethroids, and to evaluate cypermethrin as a representative pyrethroid for the purposes of a class risk assessment of the pyrethroids. The distribution of cypermethrin acute toxicity data gave 10th centile values of 10 ng/L for all organisms, 6.4 ng/L for arthropods, and 380 ng/L for vertebrates. For bifenthrin, cyfluthrin, lambda-cyhalothrin, and deltamethrin, the 10th centile values for all organisms were 15, 12, 10, and 9 ng/L, respectively, indicating similar or somewhat lower toxicity than cypermethrin. For tralomethrin and fenpropathrin, the 10th centiles were <310 and 240 ng/L, respectively. The distribution of permethrin toxicity to all organisms, arthropods, and vertebrates gave 10th centiles of 180, 76, and 1600 ng/L, respectively, whereas those for fenvalerate were 37, 8, and 150 ng/L. With the exception of tralomethrin, the distributions of acute toxicity values had similar slopes, suggesting that the variation of sensitivity in a range of aquatic nontarget species is similar. The pyrethroids have different recommended field rates of application that are related to their efficacy, and the relationship between field rate and 10th centiles showed a trend. These results support the use of cypermethrin as a reasonable worst-case surrogate for the other pyrethroids for the purposes of risk assessment of pyrethroids as a class.

Probabilistic risk assessment of cotton pyrethroids: II. Aquatic mesocosm and field studies.

Results of mesocosm and field studies with cypermethrin and esfenvalerate were analyzed and interpreted to support an ecological risk assessment of cotton pyrethroids in aquatic ecosystems. A core group of seven mesocosm studies conducted on two continents over the course of a decade were examined, and additional observations from mesocosm and field studies with these and other cotton pyrethroids were also brought to bear. The results for cypermethrin and esfenvalerate were remarkably consistent. They revealed a trend in sensitivity from amphipods, isopods, midges, mayflies, copepods, and cladocerans (most sensitive) to fish, snails, oligochaetes, and rotifers (least sensitive). With few exceptions, populations affected by pyrethroids in the mesocosms recovered to normal levels before the end of the year of exposure; most populations recovered within weeks. Factors presumed responsible for population recovery included internal refuges (areas of low exposure), resistant life stages, rapid generation times, and egg deposition by adults from outside the treated systems. Indirect effects on fish (which have been hypothesized to occur when invertebrate food sources are reduced) were not observed. The lowest-observed-adverse-effect concentrations for the overall ecosystems for cypermethrin and esfenvalerate corresponded to the 54th and 41st centiles of acute toxicity endpoints (LC50s) for arthropods measured in laboratory studies with these compounds, implying that a risk characterization based on 10th centiles would be highly conservative.

Probabilistic risk assessment of cotton pyrethroids: V. Combining landscape-level exposures and ecotoxicological effects data to characterize risks.

Since their introduction, synthetic pyrethroid insecticides have generated regulatory concerns regarding their toxicity to fish and aquatic invertebrates. In this paper we assess the potential for risks to aquatic ecosystems in cotton-growing areas, focusing on cypermethrin as a suitable representative of the pyrethroid class and static water bodies (ponds and lakes) as worst-case water bodies because of low levels of dilution. Reviews of cypermethrin effects under laboratory and field conditions have characterized the potential aquatic effects of the chemical. Also, a landscape-level exposure characterization has been conducted in a worst-case cotton-growing county, Yazoo County, Mississippi, USA, to provide a more realistic exposure characterization than is possible using standard model scenarios. Risks were characterized using the standard tier I and II approaches of the U.S. Environmental Protection Agency. In addition, a probabilistic risk assessment was conducted by comparing landscape-level exposure calculations for ponds and lakes in Yazoo County (modified tier II analysis) with distributions of laboratory effect concentrations and with data from field studies. Risk characterization using tier I and tier II models demonstrated a level of concern for certain aquatic organisms. However, modified tier II analysis showed that exposure concentrations are unlikely to exceed concentrations that might cause ecologically significant effects. Indeed, in the vast majority of cases, concentrations in the modified tier II analysis were several orders of magnitude lower than those at which effects would be predicted on the basis of laboratory and field data. The conclusion of minimal potential for adverse ecological effects was also supported by field studies, which showed that impacts on aquatic systems were negligible, even at concentrations many times higher than the modified tier II exposure concentrations.

Ecological risks of diazinon from agricultural use in the Sacramento-San Joaquin River Basins, California.

A probabilistic risk assessment was conducted to evaluate the likelihood and ecological significance of potential toxic effects of diazinon in the Sacramento-San Joaquin system. Diazinon, an organophosphorus insecticide, is used in the Sacramento-San Joaquin River Basin as a dormant spray on almonds and other tree crops, as well as for other agricultural and urban applications. Diazinon and other pesticides have been detected in the Sacramento and San Joaquin Rivers and their tributaries. Diazinon exposure was characterized based on monitoring programs conducted in 1991-94. Diazinon effects were characterized using laboratory toxicity data for 63 species, supplemented by results from field mesocosm and microcosm studies. The assessment addressed the possibility that reductions in invertebrate populations could lead to impacts on species of fish that feed on those invertebrates. The risk assessment concluded that fish in these rivers are not at risk from the direct effects of diazinon in the water. Invertebrates are at greater risk, especially in agriculturally dominated streams and drainage channels during January and February. Cladocerans--including Daphnia magna and Ceriodaphnia dubia, two common bioassay species--are especially sensitive to diazinon and other organophosphates and are likely to be subject to acute toxic effects in some locations at some times. Any ecological damage that may occur, however, is brief and limited to cladocerans. None of the fish species of concern depend on cladocerans as critical components of their diet. Invertebrates that are not affected by observed concentrations of diazinon (copepods, mysids, amphipods, rotifers, and insects) are preferred foods for fish in the Sacramento-San Joaquin system.

An ecological risk assessment for the use of Irgarol 1051 as an algaecide for antifoulant paints.

Irgarol 1051 is an algaecide used in copper-based antifoulant paints for controlling fouling organisms on the hulls of recreational and commercial watercraft. Paints containing this algaecide have been used in Europe since the mid-1980s. In 1998, the first antifouling paints containing Irgarol 1051 were registered for use in the U. S. To examine the risk that Irgarol may pose to aquatic ecosystems, a probabilistic ecological risk assessment was conducted using distributions of exposure and toxicity data. Exposure data for this assessment were derived from 11 monitoring studies (146 stations) conducted in marinas, estuaries, and coastal waters from 1992 to 1997 in six European countries. A comparison of 90th percentile concentrations pooled by station types across all regions showed that concentrations in marinas (316 ng/l) were higher than in estuaries and coastal waters (41 and 19 ng/l, respectively). A 90th percentile of 133 ng/l was reported for all pooled stations. Temporal trends showed that Irgarol concentrations typically peaked in early summer after launching of small boats with much lower concentrations occurring during the spring, fall, and winter. Toxicity data used for this risk assessment were derived primarily from unpublished studies submitted to regulatory agencies. Because Irgarol is a photosynthesis-inhibiting herbicide, it is much more toxic to plants than animals. Toxicity values for animals (fish and invertebrates) were much greater than concentrations of Irgarol reported in the environment. Therefore, a conservative approach using a distribution of only plant toxicity data (EC50s for plant growth) was used to derive a 10th percentile of 136 ng/l. This plant toxicity benchmark of 136 ng/l was used for risk characterization. Results from probabilistic analysis showed that ecological risk from Irgarol exposure was low in estuaries, coastal areas, and various open-type marinas. However, 10% or more of the plant species in enclosed marinas with low flushing rates may be exposed to Irgarol concentrations that would reduce photosynthesis activity and growth during the summer. Ecological risk to these sensitive plant species in enclosed marinas will likely be moderated because of the reversibility of Irgarol's inhibition of photosynthesis and the rapid recovery potential of plant communities. The ecological significance of marinas that generally contain numerous stressors such as trace metals, tributyltin, petroleum hydrocarbons, high nutrient concentrations, and low dissolved oxygen concentrations is a management issue that needs to be addressed.

Identification of ractopamine hydrochloride metabolites excreted in rat bile.

1. Rats dosed orally with 2.85 +/- 0.30 mg [14C]ractopamine HC1 [(1R*, 3R*), (1R*, 3S*)-4-hydroxy-alpha-[[[3-(4-hydroxyphenyl)- 1-methylpropyl]-amino]-methyl]([U-14C]benzenemethanol)hydrochloride] containing 1.44 +/- 0.15 microCi radioactivity excreted 58 +/- 7% of the administered radioactivity in the bile within 24 h. Absorption and excretion of radioactivity was rapid as 55% of the administered radiocarbon was excreted into the bile during the first 8-h collection period. 2. Radioactivity excreted in rat bile was partitioned by XAD-2 column chromatography and reverse-phase hplc into at least seven different crude metabolite fractions; metabolites representing approximately 76% of the biliary radioactivity were isolated and identified from four of the crude metabolite fractions. 3. Approximately 46% of the biliary radioactivity was identified as a sulphate-ester, glucuronic acid diconjugate of ractopamine. Identification was based on 1H-nmr and negative-ion FAB-ms spectroscopy. Enzymatic and chemical hydrolysis of the sulphate-ester followed by co-chromatography of the hydrolysis products with synthetic ractopamine mono-glucuronides, established the site of sulphation at the C-10' phenol (phenol attached to carbinol) and glucuronidation at the C-10 phenol (phenol attached to methylpropyl amine) of ractopamine. 4. A metabolite representing approximately 6% of the biliary radioactivity was identified as a ractopamine mono-sulphate conjugate by using mass spectral and 1H-nmr techniques. Sulphate was conjugated at the C-10' phenol of ractopamine and was not stereospecific. 5. Approximately 25% of the biliary radioactivity was identified as ractopamine mono-glucuronides. The major site of glucuronidation was at the C-10 phenol, but ractopamine glucuronidated at the C'-10 phenol was also present.

Depletion of residues from milk and blood of cows dosed orally and intravenously with sulfamethazine.

Cows were dosed orally (n = 4) or intravenously (n = 4) with sulfamethazine [sulmet; 4-amino-N-(4,6-dimethyl-2-pyrimidinyl)benzenesulfonamide] for 5 consecutive days (220 mg/kg of body weight on day 1 and 110 mg/kg on days 2-5). The concentrations of sulmet, N4-acetylsulfamethazine (Ac-sulmet), and the N4-lactose conjugate of sulfamethazine (lac-sulmet) were measured in milk and blood collected at 24 h intervals after the last doses of sulmet were given. The method of analysis included (1) spiking of samples with known amounts of 13C6-labeled reference compounds, (2) resolution of the 3 compounds by reversed-phase chromatography, (3) hydrolysis of lacsulmet, (4) treatment with diazomethane to yield N1-methyl derivatives, and (5) gas chromatography/mass spectrometry. The ratios of intensities of selected mass spectral ions containing 12C6 and the corresponding ions containing 13C6 were used for residue quantitation. Sulmet, which was always the most abundant residue in the blood, decreased to less than 100 ppb 4 days after the last doses were given and to less than 10 ppb 7 days after the last doses. The concentrations of sulmet in milk were approximately one fifth the concentrations of sulmet in blood. The concentrations of lac-sulmet and Ac-sulmet in milk were lower than the concentrations of sulmet in milk.

Lactose conjugation of sulphonamide drugs in the lactating dairy cow.

1. 14C-Sulphamethazine (4-amino-N-(4,6-dimethyl-2-pyrimidinyl)benzene-[U-14C]-sulphonamide; 220 mg/kg of body weight) was given orally or i.v. to lactating dairy cows. Milk collected from 0-48 h after dosing accounted for 2.0% (oral dose) and 1.1% (i.v. dose) of the total 14C-activity administered. 2. Sulphamethazine accounted for 70-79% (oral dose) and 54-75% (i.v. dose) of the total 14C in milk samples collected from 0-48 h after dosing. N4-acetylsulphamethazine accounted for 1-2% (oral dose) and 1-4% (i.v. dose) of the 14C in milk. 3. The major 14C-labelled metabolite in the milk was isolated and identified as the N4-lactose conjugate of sulphamethazine, a unique type of metabolite not previously reported. This metabolite accounted for 10-14% (oral dose) and 9-20% (i.v. dose) of the 14C-activity in the milk collected from 0-48 h after dosing with 14C-sulphamethazine. 4. N4-lactose conjugates of sulphapyridine, sulphamerazine, sulphathiazole, sulphadimethoxine and sulphaquinoxaline were present in the milk from cows orally dosed with these five sulphonamide drugs.

The isolation and identification of 14C-sulfamethazine (4-amino-n-(4,6-dimethyl-2-pyrimidinyl)[14C]benzenesulfonamide) metabolites in the tissues and excreta of swine.

Pigs were given a single oral dose of 14C-sulfamethazine (4-amino-N(I4,6-dimethyl-2-pyrimidinyl)[14C]benzenesulfonamide). Approximately 78% of the 14C was eliminated in the urine and 18% was eliminated in the feces within 192 hr after dosing. The percentage of the 14C remaining in the animals after dosing was as follows: 6 hr, 88%; 24 hr, 49%; 48 hr, 14%; 192 hr, less than 1%. The 14C-labeled compounds in the tissues and excreta were isolated by solvent extraction and by conventional and high-pressure liquid chromatography, and then derivatized and characterized by infrared and mass-spectral analysis. Chemical structures were confirmed by synthesis. The major 14C-labeled compounds in the skeletal muscle, liver and kidney were identified as sulfamethazine, N4-acetylsulfamethazine, the N4-glucose conjugate of sulfamethazine, and N-(4,6-dimethyl-2-pyrimidinyl)benzenesulfonamide (desaminosulfamethazine). The major 14C-labeled compounds in the urine and feces were identified as sulfamethazine and N4-acetylsulfamethazine.

Testing toxic substances for protection of the environment.

The Toxic Substances Control Act requires pre-production testing of chemicals for potential hazards to human and environmental health. Effective control of chemicals requires evaluations of chemical hazard that go beyond determinations of toxicity to humans to include the effects, transport, and fat of chemicals in the environemnt. Formulation of meaningful hazard evaluations depends on integrating information from tests of chemical effects, transport, and fate or by developing testing tools that integrate these factors during experimentation. Chemical effects may be acute or chronic and they may be observed individual organisms, populations or organisms, or in total ecosystems. Chemical transport through the environment depends on physico-chemical characteristics of the chemical and the medium (soil, water, or air) as well as environmental factors and biotic processes. The ultimate fate of chemicals (persistence, transformation, or degradation) is determined by numerous physical and biological processes occurring in the environment, and must be acknowledged to effectively determine the hazard. Many techniques are available for the separate and routine evaluation of the effects, transport and fate of environmental contaminants. However, separate identification of the importance and magnitude of each of these factors limits their utility in assessments of chemical hazard. The microcosm (model ecosystem) method integrates many of these tests in replicable experimental units, and may provide substantial information on chemical hazard in ecosystem context.