Root Secondary Metabolites in Populus tremuloides: Effects of Simulated Climate Warming, Defoliation, and Genotype.

Climate warming can influence interactions between plants and associated organisms by altering levels of plant secondary metabolites. In contrast to studies of elevated temperature on aboveground phytochemistry, the consequences of warming on root chemistry have received little attention. Herein, we investigated the effects of elevated temperature, defoliation, and genotype on root biomass and phenolic compounds in trembling aspen (Populus tremuloides). We grew saplings of three aspen genotypes under ambient or elevated temperatures (+4-6 °C), and defoliated (by 75%) half of the trees in each treatment. After 4 months, we harvested roots and determined their condensed tannin and salicinoid (phenolic glycoside) concentrations. Defoliation reduced root biomass, with a slightly larger impact under elevated, relative to ambient, temperature. Elevated temperature decreased condensed tannin concentrations by 21-43% across the various treatment combinations. Warming alone did not alter salicinoid concentrations but eliminated a small negative impact of defoliation on those compounds. Graphical vector analysis suggests that effects of warming and defoliation on condensed tannins and salicinoids were predominantly due to reduced biosynthesis of these metabolites in roots, rather than to changes in root biomass. In general, genotypes did not differ in their responses to temperature or temperature by defoliation interactions. Collectively, our results suggest that future climate warming will alter root phytochemistry, and that effects will vary among different classes of secondary metabolites and be influenced by concurrent ecological interactions such as herbivory. Temperature- and herbivory-mediated changes in root chemistry have the potential to influence belowground trophic interactions and soil nutrient dynamics.

A review of Agent Orange and its associated oncologic risk of genitourinary cancers.

Agent Orange is an herbicide sprayed widely in Vietnam that is linked to a variety of malignancies in as early as 1991.Since then, there has been concern for, and subsequent interest in studying, the potential connection between Agent Orange and other malignancies. In the past 2 decades, there have been significant changes in the opinion of the National Academy of Science regarding Agent Orange and certain genitourinary malignancies. Herein, we review the literature regarding the potential link between Agent Orange and various urological cancers, including prostate, bladder, testicular, and renal cancers.

[Working conditions and functional state of the organism of mechaniciandrivers under the defoliation of the cotton-plants].

In the article there are presented results of the study of the impact of working of mechanicians-drivers performing cotton-plant defoliation with a new import-substituting low-toxic defoliant denoted as «Fandef-Alo¼ on a functional state of various systems of the organism. Working conditions and the character of labor processes under the execution of defoliation were revealed to give rise in adverse shifts of physiological responses of various systems of the organism in mechanician-drivers, and the noise and the overwork labor process elevate the probability for the risk of the occurrence of occupational diseases that is indicates to the need for measures for the making labor healthy.

Colloid facilitated transport of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) to the groundwater at Ma Da area, Vietnam.

PCDD/Fs are hydrophobic organic substances and strongly sorbing to soil particles. Once adsorbed to soil particles they are believed to be virtually immobile. However, research in the last decades confirmed that strong sorbing contaminants may reach the groundwater via colloid-facilitated transport. This pathway has not been investigated before in Vietnam. Ma Da area, 100 km north of Ho Chi Minh City, was repeatedly sprayed during the Vietnam War (1962-1971) with herbicides like Agent Orange containing, beside others, the teratogenic contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). 11 surface soil samples and 12 water samples were collected in Ma Da area for analysis of PCDD/Fs in solids. Soil TCDD concentrations ranged from 1-41 ppt with a mean of 8.8 ppt and a mean I-TEQ of 9.7 ppt. Two surface water samples showed colloid bound TCDD (7 and 19 ppt). Groundwater samples showed elevated colloid bound PCDD concentrations (mean 770 ng/kg), mainly octachlorodibenzo-p-dioxin. Groundwater colloids separated by filtration did not show any TCDD. The results support that TCDD/Fs can be relocated from the top soil to the groundwater by colloidal pathway. They did not provide evidence that the dioxins bound to groundwater colloids are leftovers from the Second Indochinese War. However, this study reinforces that the colloidal transport pathway has to be included investigating the relocation of strong sorbing organic contaminants.

Glutathione S-transferase conjugation of organophosphorus pesticides yields S-phospho-, S-aryl-, and S-alkylglutathione derivatives.

Pesticide detoxification is a central feature of selective toxicity and safety evaluation. Two of the principal enzymes involved are GSH S-transferases (GSTs) and cytochrome P450s acting alone and together. More than 100 pesticides are organophosphorus (OP) compounds, but with few exceptions, their GSH conjugates have not been directly observed in vitro or in vivo. The major insecticides chlorpyrifos (CP) and diazinon are of particular interest as multifunctional substrates with diverse metabolites, while ClP(S)(OEt) 2 and the cotton defoliant tribufos are possible precursors of phosphorylated GSH conjugates. Formation of GSH conjugates by GST with GSH was studied in vitro with and without metabolic activation by human liver microsomes or P450 3A4 with NADPH. Metabolites were analyzed by liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS). Five GSH conjugates were identified from CP and chlorpyrifos oxon (CPO), i.e., GSCP and GSCPO in which the 6-chloro substituent of CP and CPO, respectively, is displaced by GSH; S-(3,5,6-trichloropyridin-2-yl)glutathione; S-(3,5-dichloro-6-hydroxypyridin-2-yl)glutathione; and S-ethylglutathione. GST of a human liver microsomal preparation but not P450 3A4 with GSH metabolized CP to GSCP. With GST and GSH, diazinon and diazoxon gave S-(2-isopropyl-4-methylpyrimidin-6-yl)glutathione and ClP(S)(OEt) 2 yielded GSP(S)(OEt) 2. With microsomes, NADPH, GST, and GSH tribufos gave GSP(O)(SBu) 2. The liver of intraperitoneally treated mice contained GSCP from CP, GSP(S)(OEt) 2 from ClP(S)(OEt) 2, and GSP(O)(SBu) 2 from tribufos. GSP(S)(OEt) 2 and GSP(O)(SBu) 2 are the first S-phosphoglutathione metabolites observed in vitro and in vivo directly by LC-ESI-MS. Nine other OP pesticides gave only O-dealkylation in the GST/GSH system. GST-catalyzed metabolism joins P450s and hydrolases as important contributors to OP detoxification.

Environmental fate and bioavailability of Agent Orange and its associated dioxin during the Vietnam War.

BACKGROUND: In 1996, the Committee on the Assessment of Wartime Exposure to Herbicides in Vietnam of the National Academy of Sciences' Institute of Medicine (IOM) issued a report on an exposure model for use in epidemiological studies of Vietnam veterans. This exposure model would consider troop locations based on military records; aerial spray mission data; estimated ground spraying activity; estimated exposure opportunity factors; military indications for herbicide use; and considerations of the composition and environmental fate of herbicides, including changes in the TCDD content of the herbicides over time, the persistence of TCDD and herbicides in the environment, and the degree of likely penetration of the herbicides into the ground. When the final report of the IOM Committee was released in October 2003, several components of the exposure model envisioned by the Committee were not addressed. These components included the environmental fate of the herbicides, including changes in the TCDD content over time, the persistence of TCDD and herbicides in the environment, and the degree of likely penetration of herbicides into the ground. This paper is intended to help investigators understand better the fate and transport of herbicides and TCDD from spray missions, particularly in performing epidemiological studies. METHODS: This paper reviews the published scientific literature related to the environmental fate of Agent Orange and the contaminant, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), and discusses how this affected the potential exposure to TCDD of ground troops in Vietnam. Specifically, the mechanisms of dissipation and degradation as they relate to environmental distribution and bioavailability are addressed. RESULTS: The evaluation of the spray systems used to disseminate herbicides in Vietnam showed that they were capable of highly precise applications both in terms of concentrations sprayed and area treated. Research on tropical forest canopies with leaf area indices (a measure of foliage density) from 2 to 5 indicated that the amount of herbicide and associated TCDD reaching the forest floor would have been between 1 and 6% of the total aerial spray. Studies of the properties of plant surface waxes of the cuticle layer suggested that Agent Orange, including the TCDD, would have dried (i.e., be absorbed into the wax layer of the plant cuticle) upon spraying within minutes and could not be physically dislodged. Studies of Agent Orange and the associated TCDD on both leaf and soil surface have demonstrated that photolysis by sunlight would have rapidly decreased the concentration of TCDD, and this process continued in shade. Studies of 'dislodgeable foliar residues' (DFR, the fraction of a substance that is available for cutaneous uptake from the plant leaves) showed that only 8% of the DFR was present 1 hr after application. This dropped to 1% of the total 24 hrs after application. Studies with human volunteers confirmed that after 2 hrs of saturated contact with bare skin, only 0.15-0.46% of 2,4,5-T, one of the phenoxy acetic acid compounds that was an active ingredient of Agent Orange, entered the body and was eliminated in the urine. CONCLUSIONS: The prospect of exposure to TCDD from Agent Orange in ground troops in Vietnam seems unlikely in light of the environmental dissipation of TCDD, little bioavailability, and the properties of the herbicides and circumstances of application that occurred. Photochemical degradation of TCDD and limited bioavailability of any residual TCDD present in soil or on vegetation suggest that dioxin concentrations in ground troops who served in Vietnam would have been small and indistinguishable from background levels even if they had been in recently treated areas. Laboratory and field data reported in the literature provide compelling evidence on the fate and dislodgeability of herbicide and TCDD in the environment. This evidence of the environmental fate and poor bioavailability of TCDD from Agent Orange is consistent with the observation of little or no exposure in the veterans who served in Vietnam. Appreciable accumulation of TCDD in veterans would have required repeated long-term direct skin contact of the type experienced by United States (US) Air Force RANCH HAND and US Army Chemical Corps personnel who handled or otherwise had direct contact with liquid herbicide, not from incidental exposure under field conditions where Agent Orange had been sprayed.

Dissipation of the defoliant tribufos in cotton-producing soils.

Soil dissipation of the cotton defoliant tribufos was measured in laboratory incubations and on 0.2-ha research plots. Computed 50% dissipation time (DT(50)) using nonlinear and linear kinetic models ranged from 1 to 19 days. Data indicated that exchangeable soil aluminum inhibited tribufos-degrading soil organisms. Nevertheless, measured DT(50) values were 40 to 700 times less than the aerobic soil half-life (t(1/2)) values used in recent tribufos risk assessments. DT(50) values suggest that risk estimates were overstated. However, edge-of-field runoff concentrations measured on research plots exceeded invertebrate LOECs, thus some aquatic risk is indicated. Field data also suggested that volatilization may be a significant soil dissipation pathway. From this result, we conclude that volatilization should be included in simulation models used for pesticide registration. This will likely improve the accuracy of model outputs for products such as tribufos. Potential volatilization losses indicate a need to evaluate the atmospheric behavior of tribufos.

[Toxicological and hygienic evaluation of sardor, a new defoliant agent and its occupational standardization]. / Toksikologo-gigienicheskaia otsenka novogo defolianta khlopchatnika Sardor i ego gigienicheskoe normirovanie.

Study of the toxicity of Sardor, a new cotton defoliant, showed that it is a low toxic compound. Hygienic norms and regulations for its use in agriculture were developed.

Relation of serum 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) level to hematological examination results in veterans of Operation Ranch Hand.

The authors studied indices of hematologic function and exposure to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in Vietnam War veterans of Operation Ranch Hand--the Air Force unit responsible for the aerial spraying of Agent Orange and other herbicides in Vietnam. The herbicides were contaminated with TCDD. The authors measured TCDD serum levels in 1987 or later and extrapolated the result to the time of service in Vietnam. The authors studied serum TCDD level in relation to red blood cell count, hemoglobin, hematocrit, mean corpuscular volume, white blood cell count, platelet count, and erythrocyte sedimentation rate at each of 4 physical examinations. Compared with veterans not involved in Operation Ranch Hand, those with the highest TCDD levels in Operation Ranch Hand had mean corpuscular volumes that were about 1% higher and platelet counts that were about 4% higher. These small increases were unlikely to be of clinical significance and may not have been caused by TCDD.

Influence of nitrogen fertilization and defoliation frequency on nitrogen constituents and feeding value of annual ryegrass.

Two experiments were conducted to determine the seasonal effects of N fertilizer (NF) and defoliation interval (DI) on specific N fractions within annual ryegrass (AR) and overall usage of AR N by growing lambs. In Exp. 1, NF (0, 112, 224, and 336 kg of N/ha) and DI of 2, 4, or 6 wk were factorially applied to AR plots. Both decreasing DI and increasing NF increased N levels in AR in a manner that depended on harvest date (NF or DI x harvest date interaction, P < .05). The proportions of .2% NaOH soluble N or soluble protein N were not affected (P > .05) by NF or DI. Although NF had no effect (P > .05) on in situ disappearance of DM, decreasing the DI seemed to reduce the severity of the season-induced reduction in DM disappearance (DI x harvest date interaction, P = .04). In Exp. 2, NF (0 or 224 kg of N/ha) and a DI of 2 or 6 wk were factorially applied to AR plots. Fresh, frozen AR was fed in semipurified diets (48% of DM as AR) to four wether lambs (23 +/- 1.3 kg) using a 4 x 4 Latin square. Diets including AR had greater ruminal DM and plant N digestibilities when AR had a 2-wk vs a 6-wk DI with NF but had reduced digestibilities when AR had a 2-wk vs a 6-wk DI without NF.(ABSTRACT TRUNCATED AT 250 WORDS)

[Effect of water contamination with surface active substances and plant protecting agents on aquatic organisms]. / Wplyw zanieczyszczenia wód substancjami powierzchniowo-czynnymi i srodkami ochrony roslin na organizmy wodne.

The purpose of the study was establishing in what degree the presence of surface-active substances affects the influence of herbicides present in surface waters on aquatic organisms. The study was carried out under laboratory conditions using as herbicides promethrin (triazine group) and dichlorophenoxy-acetate sodium (2,4 D), and detergents - sodium alkylsuphonate ABS and non-ionic detergent Rokafenol N8P7. The effect of these substances was studied on the test organisms from own cultures - Daphnia magna Straus, larvae of insects Chironomus plumosus L, and young fish Lebistes reticulatus. The study showed that promethrin was the herbicide with stronger action on the studied organisms than 2,4 D. The presence of single detergents and their mixtures increased promethrin effects by 10-13% on the testes invertebrates even in concentrations permitted in surface waters. The toxic effect of the herbicide 2,4 D was potentiated by detergents in much higher concentrations, exceeding the permitted values. Contamination of surface waters with detergents may endanger the trophic chain of aquatic biocenoses.