Duplicate sampling reproducibility of atmospheric residues of herbicides for paired pan and high-volume air samplers

The reproducibility of collection of atmospheric residues of the herbicides 2,4-D and triallate as bulk (wet plus dry) deposition samples by paired pan samplers and as particulate (filter) and vapour (PUF/XAD-2 resin cartridge) samples by paired high-volume air samplers was determined. Variability of herbicide concentrations in paired bulk deposition samples was within 25% for 65 and 80% of the samples for 2,4-D and triallate, respectively, with approximately 90% of the paired samples being within a factor of 2 for both herbicides. The vapour samples of 2,4-D and triallate showed similar reproducibilities. The highest reproducibility was observed for the filter samples with 92% of the paired data sets for 2,4-D being within 25% variability. No triallate was detected in the filter samples.     

Evaluation of polyurethane foam as a trapping medium for herbicide vapor in air monitoring and worker inhalation studies

Polyurethane foam was an efficient adsorbent for trapping vapors of butyl esters of 2,4-D (2,4-dichlorophenoxyacetic acid) and triallate (S-(2,3,3-trichloroallyl)diisopropylthiocarbamate) in high volume air monitoring studies and of butyl esters of 2,4-D, iso-octyl ester of 2,4-D, n-butyl ester of 2,4,5-T (2,4,5-trichlorophenoxyacetic acid), bromoxynil octanoate (2,5-dibromo-4-hydroxybenzonitrile), triallate, and trifluralin (alpha, alpha, alpha-trifluoro-2,6-dinitro-N-N-dipropyl-p-toluidine) in short-term, low volume, worker inhalation exposure studies. The collected herbicide vapor was readily desorbed under soxhlet extraction with n-hexane and subsequently analyzed with electron-capture GLC. The overall efficiencies, for both trapping and extraction, were over 90%, using a single plug, for all herbicides, except triallate. In the case of triallate, two plugs in series were required for efficient trapping under the high volume air monitoring situation.     

Chlorinated herbicide (triallate) dehalogenation by iron powder

The reductive degradation of a chlorinated herbicide by iron powder was investigated at lab scale. The studied substrate was triallate (S-2,3,3-trichloroallyl di-isopropyl thiocarbamate) which contains a trichloroethylene moiety potentially reducible by zero-valent iron. Degradation reactions were carried out in batch, at 25 degrees C, in the absence of oxygen, by contacting electrolytic iron powder (size range: 20-50 microm) with a triallate aqueous solution (2.5 mgl(-1)). Herbicide decay, corresponding evolutions of TOC, TOX and chloride ion release were regularly monitored throughout the reactions. Furthermore, the main degradation by-products were identified by HPLC/MS. The results showed that, after 5 days, herbicide degradation extent was about 97% and that the reaction proceeded through the formation of a dechlorinated alkyne by-product (S-2-propinyl di-isopropyl thiocarbamate) resulting from the complete dechlorination of triallate. The subsequent reduction of such an alkyne intermediate gave S-allyl di-isopropyl thiocarbamate as main end by-product. The identified by-products suggested that dechlorination took place mainly via reductive beta-elimination. However, as traces of dichloroallyl di-isopropyl thiocarbamate were also detected, a role, although minor, was assigned even to hydrogenolysis in the overall dechlorination process.     

Volatilisation of crop protection chemicals from crop and soil surfaces under controlled conditions--prediction of volatile losses from physico-chemical properties

Volatilisation of crop protection chemicals from soil and crop surfaces is one of a number of processes that may contribute to their dissipation in the environment. Therefore, information on the potential of a chemical to volatilise from these surfaces is required by international and national registration authorities. This paper reports the results of more than 190 experiments, which were carried out with 80 different crop protection chemicals under controlled conditions (laboratory and/or greenhouse) according to the BBA guideline. Percent loss values observed during 24 h after application are reported for 123 soil and 71 crop volatility studies. Generally, volatile losses from crop surfaces were found to be greater than from soil surfaces under comparable experimental conditions. It has been previously proposed that volatile losses from soil surfaces, from crops, and from aqueous systems can be estimated from physico-chemical parameters. The data are therefore analysed to determine whether a correlation exists between volatilisation and physico-chemical parameters, such as vapour pressure, Henry's law constant, water/air and soil/air distribution coefficients. It was found that these parameters can be used to make reasonable predictions of volatile losses from crop and soil surfaces, which can be expected for crop protection chemicals under controlled conditions. Vapour pressure was the best predictor of losses from soil and crops. The use of the soil/air distribution coefficient is an alternative for predicting/estimating the volatility potential of a chemical from soil. Based on direct measurements, no noticeable volatility can be expected from compounds with a vapour pressure below 10(-3) Pa from soil and 10(-4) Pa from crops, this is fully confirmed by indirect measurements. A tiered volatility testing scheme including appropriate trigger values is proposed.     

Sorption and leaching of flucetosulfuron in soil

Abstract

The adsorption–desorption and leaching of flucetosulfuron, a sulfonylurea herbicide, was investigated in three Indian soils. Freundlich adsorption isotherm described the sorption mechanism of herbicide with adsorption coefficients (K_f) ranging from 17.13 to 27.99 and followed the order: Clayey loam?>?Loam?>?Sandy loam. The K_f showed positive correlation with organic carbon (OC) (r?=?0.910) and clay content (r?=?0.746); but, negative correlation with soil pH (r = ?0.635). The adsorption isotherms were S-type suggesting that herbicide adsorption was concentration dependent and increased with increase in concentration. Desorption followed the sequence: sandy loam?>?clayey loam?>?loam . Hysteresis (H) was observed in all the three soils with H?<?1. Leaching of flucetosulfuron correlated positively with the soil pH; but, negatively with the OC content. Sandy loam soil (OC- 0.40%, pH ?7.25) registered lowest adsorption and highest leaching of flucetosulfuron while lowest leaching was found in the loam soil (pH ? 7.89, OC ? 0.65%). The leaching losses of herbicide increased with increase in the rainfall intensity. This study suggested that the soil OC content, pH and clay content played important roles in deciding the adsorption–desorption and leaching behavior of flucetosulfuron in soils.     

Factors affecting ammonia volatilisation from a rice-wheat rotation system

Some of the major factors influencing ammonia volatilisation in a rice wheat rotation system were studied. A continuous airflow enclosure method was used to measure NH3 volatilisation in a field experiment at an agricultural college in Jiangsu Province. The five treatments comprised application rates of 0, 100, 200 or 300 kg N ha(-1) as urea, per growing season with rice straw amendment when wheat was sown, and 200 kg N ha(-1) without rice straw amendment. There were three replicates in a randomised block design. Ammonia volatilisation was measured immediately after urea application in the three consecutive years 1995 to 1997. The results show that N losses through NH3 volatilisation accounted for 4-19% of N applied during the wheat growing season and for 5-11% during the rice growing season. Ammonia volatilisation was affected significantly by soil moisture and temperature before and after fertiliser application during the wheat growing season. The ratio of volatilised NH3-N to applied N after urea application during the rice growing season was as follows: top-dressing at the onset of tillering > top-dressing at the start of the booting stage > basal fertilization. The results also show that the amount of N lost through NH3 volatilisation increased with increasing N application rate, but the ratio to applied N was not affected significantly by N application rate. Amendment with rice straw had no significant effect on NH3 volatilisation.     

Dissipation and runoff transport of metazachlor herbicide in rapeseed cultivated and uncultivated plots in field conditions

The environmental fate of metazachlor herbicide was investigated under field conditions in rapeseed cultivated and uncultivated plots, over a period of 225 days. The cultivation was carried out in silty clay soil plots with two surface slopes, 1 and 5 %. The herbicide was detectable in soil up to 170 days after application (DAA), while the dissipation rate was best described by first-order kinetics and its half-life ranged between 10.92 and 12.68 days. The herbicide was detected in the soil layer of 10–20 cm from 5 to 48 DAA, and its vertical movement can be described by the continuous stirred tank reactor (CSTR) in series model. Relatively low amounts of metazachlor (less than 0.31 % of the initial applied active ingredient) were transferred by runoff water. More than 80 % of the total losses were transferred at the first runoff event (12 DAA), with herbicide concentrations in runoff water ranging between 70.14 and 79.67 μg L⁻¹. Minor amounts of the herbicide (less than 0.07 % of the initial applied active ingredient) were transferred by the sediment, with a maximum concentration of 0.57 μg g⁻¹ (12 DAA), in plots with 5 % inclination. Finally, in rapeseed plants, metazachlor was detected only in the first sampling (28 DAA) at concentrations slightly higher than the limit of quantification; when in seeds, no residues of the herbicide were detected.

     

Dissipation of s-triazines and thiocarbamates from soil as related to soil moisture content

Half-lives (t1/2) of two soil incorporated s-triazines (atrazine and prometon) and two thiocarbamate (EPTC and triallate) herbicides were determined in relation to soil moisture content in two California soils. Treated soils were incubated at three moisture levels in aerated glass vials at 25 +/- 1 degree C and were analyzed at 0, 7, 16, 28, 56 and 112 day intervals. Loss of herbicides in all treatments followed first-order kinetics. The t1/2-values of all herbicides decreased with increasing soil moisture and followed an empirical equation, t1/2 = aM(-b) (where t1/2 is half-life; M the moisture content; and a and b are constants). Soil moisture had a greater effect on carbamates than on s-triazines . Prometon exhibited the longest half-life in both soils, whereas EPTC was least persistent in one soil and atrazine in another. The t1/2-values for atrazine, prometon, EPTC, and triallate with medium moisture levels and 10 microg/g concentration were 34.6, 43.2, 25.4 and 38.1 days in sandy loam and 26.5, 44.4, 44.1 and 25.9 days in loamy sand, respectively. Disappearance of 50% of the applied concentrations of most of the herbicide-soil combinations (except EPTC and triallate in one soil) took longer for lower initial concentrations (1 microg/g) than for higher concentrations (10 microg/g).     

Effect of soil sterilization by mercuric chloride on herbicide sorption by soil

Microbial inhibitors such as mercuric chloride are frequently used to sterilize soil or soil-water slurries in experimental studies on the fate of xenobiotics in the environment. This study examined the influence of mercuric chloride additions to soil-water slurries on the sorptive behaviour of a phenoxy herbicide (2,4-D) in soil. The results demonstrated that mercuric chloride strongly decreased the capacity of the soil to retain herbicides, and that the interference of mercuric chloride with herbicide sorption increased with increasing soil organic carbon contents. Because of the competitive sorption between mercuric chloride and the phenoxy herbicide, we conclude that mercuric chloride may not be a good soil sterilization procedure for use in xenobiotic fate studies.     

The effect of temperature and solar radiations on volatilisation, mineralisation and degradation of [14C]-DDT in soil

The influence of temperature and solar radiations on the rapid dissipation of DDT from tropical soils was studied by quantifying volatilisation, mineralisation, binding and degradation of ((14)C)-p,p'-DDT in a sandy loam soil. The bulk of the DDT loss occurred by volatilisation, which increased fivefold when the temperature changed from 15 to 45 degrees C. Degradation of DDT to DDE was also faster at higher temperatures. Mineralisation of DDT, though minimal, increased with temperature and time. Higher temperatures also enhanced binding of DDT to soil. Flooding the treated soil further increased volatilisation and degradation, although mineralisation was greatly reduced. Exposure of flooded and unflooded soils treated with DDT to sunlight in quartz, glass and dark tubes for 42 days during summer resulted in significant volatile losses. Volatilisation in the quartz tubes was nearly twice as great as that in the dark tubes The volatilised organics from the quartz tubes contained larger amounts of p,p'-DDE than the glass and dark tubes. Higher rates of volatilisation and degradation were found in flooded soils. Also significant quantities of p,p'-DDD were detected in addition to DDE. The data clearly show that volatilisation is the major mechanism for the rapid dissipation of DDT from Indian soils.     

Measured and predicted volatilisation fluxes of PCBs from contaminated sludge-amended soils

A laboratory experiment was carried out to measure volatilisation fluxes of polychlorinated biphenyls (PCBs) from sewage sludge-amended soils. The most commonly practised methods of applying sludge to agricultural land in the UK, namely, surface application, ploughing in to soil and subsurface injection, were simulated inside glass experimental chambers using an anaerobically digested sludge and a sandy loam soil. Humidified air was blown over the surface of the soil/sludge in the chambers for a period of 32 days, in order to sample a sufficient air volume to detect the volatilising PCBs. The resulting PCB volatilisation fluxes from the different sludge application methods were quantified and compared. Volatilisation fluxes of individual congeners were generally highest for the surface sludge (1-cm depth) application and slightly lower for the plough layer (5-cm depth) application. Fluxes from the subsurface layer of sludge (5-cm depth) were only quantified for the lightest congeners near to the end of the experimental run-time. Results from a multiple regression analysis showed that volatilisation fluxes of PCBs from the surface application are highly dependent on both the sludge concentration and the log of the octanol-air partition coefficient (K(OA)). A well-known soil volatilisation model, developed by Jury et al., was adapted and used to predict fluxes for the different sludge application methods during the experiment. The model predicted volatilisation fluxes that were reasonably comparable to measured fluxes for some congeners, but for others predicted fluxes that were more than an order of magnitude lower than measured fluxes. The model predicted similar loss kinetics to those observed in the experiment. Possible reasons for the dissimilarity between measured and predicted fluxes include inaccuracies in model input parameters and the fact that the models were not developed for predicting fluxes from sludge-amended soils.     

Sorption of herbicides in relation to soil variability and landscape position

Using the soil-water sorption partitioning coefficient (Kd), this study quantified the spatial variation of 2,4-D sorption by soil in an undulating-to-hummocky terrain landscape near Minnedosa, MB, Canada. Herbicide sorption was most strongly related to soil organic matter content and slope position, with greatest sorption occurring in lower landscape positions with greater soil organic matter content. The relation between sorption and slope position was more pronounced under conventional tillage (CT) than under long-term zero-tillage (ZT). Using multivariate regression and three independent variables (soil organic matter content, soil clay content and soil pH), the prediction of herbicide sorption by soil was very good for CT (R2 = 0.89) and adequately for ZT (R2 = 0.53).     

Atrazine and metolachlor residues in brookston Cl following conventional and conservation tillage culture

Atrazine and metolachlor are extensively used in Ontario, Canada for control of broadleaf weeds and annual grasses in corn. Conservation tillage may alter the physical and biological environment of soil affecting herbicide dissipation. The rate of dissipation of these two herbicides in soil from conventional, ridge and no-tillage culture was followed. Herbicide dissipation was best described by first order reaction kinetics. Half life, the time for herbicide residues to dissipate to half their initial concentration, was unaffected by tillage. Half life for atrazine and metolachlor was similar and ranged from 31 to 66 d. The rate of dissipation decreased in dry years when soil moisture content was low. In a dry year, herbicide residues during the growing season were significantly greater on ridge tops than in the other tillage treatments. However, after harvest no differences in herbicide residues were detected among tillage treatments. Residues of atrazine (6 to 9% of applied) and metolachlor (4 to 6%) were detected in soil before planting a year after application. De-ethyl atrazine, the primary degradation product of atrazine, increased in concentration during the growing season with the greatest concentrations measured at harvest and in years when atrazine dissipated fastest. De-ethyl atrazine one year after application accounted for about 12% of the remaining triazine residue. These herbicide residues would not be phytotoxic to subsequent crops but are a potential source for leaching to ground and surface waters.     

Nitrous oxide and dinitrogen emissions from soil under different water regimes and straw amendment

In a laboratory study, soil amended with and without wheat straw (2.8 g kg(-1) soil) was incubated under 70% water holding capacity (WHC), continuously flooded and flooded/drained cycle conditions at 30 degrees C for 51 days. Dinitrogen and N2O evolution and ammonia volatilisation were measured during the incubation. Extractable NH4+-N and NO3--N were determined at the end of the incubation. Entrapped N2, N2O, and dissolved NH4+-N and NO3--N in drainage water were measured in the flooded/drained cycle treatment when the floodwater was drained. The results indicated that N loss through ammonia volatilisation was undetected in all treatments due to the low soil pH value (pHH2O= 5.87) and no air movement. The recovery of urea-15N as N2 was lowest in the continuously flooded treatments (0.75% and 0.96% with and without straw amendment, respectively), highest in the 70% WHC treatments (5.65% and 4.41%, respectively), and intermediate in the flooded/drained cycle treatments (1.79% and 2.65%, respectively). The recovery of urea-15N as N2O was in the same order as that of N2, negligible in the continuously flooded treatments, 0.01% and 0.07% in the flooded/drained cycle treatments, and 1.29% and 2.23% in the 70% WHC treatments, respectively. Peak N2O evolution rates were observed after the floodwater was drained but no substantial evolution was found after the soil was reflooded following drained periods. However, peak N2 evolution rates were observed after the onset of both drainage and re-flooding. Considerable quantities of N2 but no detectable N2O were entrapped in the flooded soil.     

Analysis of some organochlorine pesticides in an urban atmosphere (Strasbourg, east of France)

High volume samples of urban air have been collected in Strasbourg, a big city situated in the east of France, for the evaluation of the contamination by organochlorine pesticides. Pesticides (p,p'-DDT, p,p'-DDD, p,p'-DDE, aldrin, dieldrin, endrin, gamma-HCH, cis-chlordane, trans-chlordane, alpha-endosulfan, beta-endosulfan, hexachlorobenzene, heptachlor and some of their metabolites: alpha-HCH, 2,4'-DDT, 2,4'-DDD and 2,4'-DDE) were analysed by GC-ECD. Prior to analysis, samples were Soxhlet extracted with a mixture of n-hexane/methylene chloride. The analysis of samples collected in 2001 (n = 6), 2002 (n = 7) and 2003 (n = 5) shows that alpha-HCH and gamma-HCH were detected in all samples (between 0.05 and 4 ng m(-3) and between 0.01 and 1 ng m(-3), respectively) along with aldrin and dieldrin at lower concentrations (between 0.01 and 0.08 ng m(-3) and between 0.02 and 0.09 ng m(-3), respectively). Other pesticides were detected very randomly at very low concentrations. The calculation of the alpha/gamma-HCH ratio shows that hexachlorocyclohexane measured in the atmosphere have a local origin and come probably from contaminated soil by volatilisation. alpha and beta-endosulfan were practically not detected in samples collected in 2001 and 2002 while they were always measured in the gas phase in samples from 2003. This observation can be explained by an increase of volatilisation with the increase of the air temperature. In July, temperature were higher (between 17 and 30 degrees C in climatic station) than in March-May 2001 and 2002 (between 2 and 19 and between 2 and 10, respectively).     

建筑物对高架点源大气污染物扩散影响的模拟研究

运用数值方法对城市中高架点源排放大气污染物的扩散规律进行了模拟研究,在计算区域内建立了三维数学模型,并将拉格朗日法描述的颗粒轨道模型耦合到风场。本研究计算了地面风速为3 m/s时的大气流场,并模拟研究了该风场条件下气体污染物的扩散和固体颗粒污染物的运动轨迹。通过分析模拟结果,给出了高架点源中排放的气体污染物的扩散区域和固体颗粒污染物运动轨迹的变化规律。     

Chiral signatures of PCB#s 95 and 149 in indoor air, grass, duplicate diets and human faeces

Chiral signatures of PCB#s 95 and 149 are reported for indoor air, grass, omnivorous and vegan duplicate human diet homogenates, and human faeces. Comparison of chiral signatures of both congeners in grass with those reported previously for outdoor air (measured at a height of 1.5 m) and soil at the same location suggest that volatilisation of PCBs present in soil may exert a significant influence on concentrations in grass. Duplicate diet homogenates display racemic signatures for both congeners. Alongside the racemic signatures in both outdoor and indoor air, this implies that human intake via diet and inhalation is racemic, and that the previously observed variation between individuals in the extent of enantioselective degradation in human liver samples indicates possible inter-individual variation in ability to metabolise PCBs. Chiral signatures of PCB# 95 in the 10 human faecal samples analysed indicate 8 to be racemic, but 2 to display an excess of the 2nd eluting enantiomer. This is consistent with the excess of the 1st eluting enantiomer reported elsewhere for human liver samples, as it implies enantioselective excretion of the 2nd eluting enantiomer. However, the racemic residues for PCB# 95 in the majority of faecal samples are a possible indication that enantioselective interaction of chiral PCBs with cytochrome P450 occurs slowly. The racemic or near-racemic signatures observed for PCB# 95 and 149 in indoor air match closely those in outdoor air, but differ from those in soil, adding to the weight of evidence that ventilation of indoor air is a far more significant contributor to outdoor air concentrations than volatilisation of PCBs from soil.     

Volatility of TCDD and PCB from soil

Volatilisation fluxes of 2,3,7,8-tetrachlorodibenzodioxin and Aroclors 1242, 1254 and 1260 were estimated from the model of Jury et.al., developed for compounds with similar physical properties. The influence of soil water content, soil organic matter and water evaporation was investigated. Increasing soil organic matter decreased the volatilisation flux of all four chemicals. Water evaporation was accompanied by increased fluxes, implying that the chemicals were susceptible to wicking. The trends observed were in qualitative agreement with field and laboratory studies. The predicted fluxes serve as a basis for comparing their volatilisation behaviour against pesticides and other homologues, and for the construction of models describing the environmental fate of these compounds.     

Soil-air exchange of organochlorine pesticides in the Southern United States

Soil samples were collected from 30 farms in Alabama, Louisiana and Texas during 1999-2000 to determine residues of organochlorine pesticides (OCPs). One or more of the DDT compounds (p,p'-DDT, o,p'-DDT, p,p'-DDD, p,p'-DDE, o,p'-DDE) was above the quantitation limit (0.1 ng g(-1) dry weight) in every soil, and toxaphene was above the quantitation limit (3 ng g(-1)) in 26 soils. Chlordanes, dieldrin and hexachlorocyclohexane (HCH) isomers occurred less frequently (quantitation limits 0.1 ng g(-1) for dieldrin and 0.05 ng g(-1) for chlordanes and HCHs). OCPs were measured in air at 40 cm above the soil at selected farms to investigate soil-air partitioning. Concentrations of OCPs in air were positively and significantly (P<0.001-0.004) correlated to soil concentrations for toxaphene, p,p'-DDT, o,p'-DDT, p,p'-DDE, dieldrin, and trans-nonachlor. The regression was weaker (P=0.022) for cis-chlordane and not significant for trans-chlordane (P=0.43) nor gamma-HCH (P=0.80). Approach to soil-air equilibrium was assessed by calculating fugacities in the soil and air (f(s) and f(a)) for samples with quantifiable residues in both compartments. The fugacity fraction f(s)=0.5 at equilibrium and is <0.5 or >0.5 for net deposition and net volatilisation, respectively. Fugacity fractions varied greatly for different soil-air pairs, reflecting generally disequilibrium conditions. Mean fugacity fractions indicated near-equilibrium for some OCPs (p,p'-DDE, chlordanes, trans-nonachlor and dieldrin) and net volatilisation for others (p,p'-DDT, o,p'-DDT, toxaphene, gamma-HCH). Chiral analysis showed that enantioselective degradation of (+) or (-) o,p'-DDT in soil was accompanied by enrichment or depletion of the corresponding enantiomers in the overlying air, although there appeared to be some dilution by racemic o,p'-DDT from regional air transport.     

Uptake of terbuthylazine and its medium polar metabolites into maize plants

The uptake of terbuthylazine and its medium polar metabolites into maize plants under outdoor conditions is investigated. For this purpose, a dynamical fate model consisting of soil, plant and air is developed. The model calculations are compared with experimental results of outdoor lysimeter tests, carried out with¹⁴C-labelled herbicide applied to sandy agricultural soil at a single application rate of 890 g/ha. Approximately 0.3 % of the applied activity remains in all the plants after the vegetation period. The model predicts that about three times that amount is volatilized from the plants into the air. Activity uptaken from soil and volatilized from plant surface into air is predominately associated with metabolites. During the whole vegetation period the fraction of unchanged terbuthylazine in the plants is very small (less than 1 % of the extractable activity).