Comparison of surface emissions and subsurface distribution of cis- and trans-1,3-dichloropropne and chloropicrin in sandy field beds covered with four different plastic films

The purpose of this study was to conduct a field study at a Florida field site on surface emissions and subsurface distribution of cis-and trans-1,3-dichloropropene (1,3-D) and chloropicrin (CP) in raised beds injected with Telone C35 with four replications. A total of 16 beds were applied with Telone C35 by chisel injection and covered with four different plastic films, 4 beds for each film. Each bed was installed with five 20-cm long soil pore air probes and a surface air collection pan at arbitrarily locations along the length of each bed for sampling soil pore air and surface air, respectively, for analysis of the three biologically active compounds, cis- and trans-1,3-D and CP. We found that average concentrations of the three compounds at 20-cm depth among the beds covered with four different plastic films generally were not statistically different. Among the four beds covered with the same plastic film, average concentrations of the three compounds were statistically different only in the four metallic PE covered beds at 5 and 24 hours after injection. Volatilization rates of the three compounds among the beds covered with four different plastic films, with the exception of CP at 48 hours after injection, were not statistically different. It appeared that initial upward diffusion and volatilization flux were influenced by solar radiation. Initial subsurface concentrations of the three compounds and volatilization flux, especially cis-1,3-D, were greater in the beds on the east side of the field than that in the beds on the west side of the field. Whether or not difference in initial subsurface concentrations of the compounds between east side beds and west side beds may influence fumigant efficacy remains to be determined.     

Atmospheric volatilization and distribution of (Z)- and (E)-1,3-dichloropropene in field beds with and without plastic covers

The fumigant 1,3-dichloropropene (1,3-D) is considered to be a potential replacement for methyl bromide when methyl bromide is phased out in 2005. This study on surface emissions and subsurface diffusion of 1,3-D in a Florida sandy soil was conducted in field beds with or without plastic covers. After injection of the commercial fumigant Telone II by conventional chisels to field beds at 30cm depth which were covered with polyethylene film (PE), virtually impermeable film, or no cover (bare), (Z)- and (E)-1,3-D rapidly diffused upward. Twenty hours after injection, majority of (Z)- and (E)-1,3-D had moved upward from 30 cm depth to the layer of 5-20 cm depth. Downward movement of the two isomers in the beds with or without a plastic cover was not significant. (Z)-1,3-D diffused more rapidly than (E)-1,3-D. Virtually impermeable films (VIF) had a good capacity to retain (Z)- and (E)-1,3-D in soil pore air space. Vapor concentrations of the two isomers in the shallow subsurface of the field bed covered with VIF were greater than that in the two beds covered with polyethylene film (PE) or no cover (bare). In addition, VIF cover provided more uniform distribution of (Z)- and (E)-1,3-D in shallow subsurface than PE cover or no cover. Virtually impermeable film also had a better capability to retard surface emissions of the two isomers from soil in field beds than PE cover or no cover.     

Emissions and distribution of methyl bromide in field beds applied at two rates and covered with two types of plastic mulches

A field experiment was conducted to compare two plastic mulches and two application rates on surface emissions and subsurface distribution of methyl bromide (MBr) in field beds in Florida. Within 30 minutes after injection of MBr to 30 cm depth, MBr had diffused upward to soil surface in all beds covered with polyethylene film (PE) or virtually impermeable film (VIF) and applied at a high rate (392 kg/ha) and a low rate (196 kg/ha). Due to the highly permeable nature of PE, within 30 minutes after injection, MBr volatilized from the bed surfaces of the two PE-covered beds into the atmosphere. The amount of volatilization was greater for the high rate-treatment bed. On the other hand, volatilization of MBr from the bed surfaces of the two VIF-covered beds were negligible. Volatilization losses occurred from the edges of all the beds covered with PE or VIF and were greater from the high rate-treatment beds. Initial vertical diffusion of MBr in the subsurface of the beds covered with PE or VIF was mainly upward, as large concentrations of MBr were detected from near bed surfaces to 20 cm depth in these beds 30 minutes after injection and little or no MBr was found at 40 cm depth. The two VIF-covered beds exhibited greater MBr concentrations and longer resident times in the root zone (0.5–40 cm depth) than corresponding PE-covered beds. Concentrations of MBr in the root zone of the high rate-treatment beds were 3.6–6.1 times larger than the low rate-treatment beds during the first days after application. In conclusion, VIF promoted retention of MBr in the root zone and, if volatilization loss from bed edges can be blocked, volatilization loss from VIF-covered beds should be negligible.     

Emissions and distribution of methyl bromide in field beds applied at two rates and covered with two types of plastic mulches

A field experiment was conducted to compare two plastic mulches and two application rates on surface emissions and subsurface distribution of methyl bromide (MBr) in field beds in Florida. Within 30 minutes after injection of MBr to 30 cm depth, MBr had diffused upward to soil surface in all beds covered with polyethylene film (PE) or virtually impermeable film (VIF) and applied at a high rate (392 kg/ha) and a low rate (196 kg/ha). Due to the highly permeable nature of PE, within 30 minutes after injection, MBr volatilized from the bed surfaces of the two PE-covered beds into the atmosphere. The amount of volatilization was greater for the high rate-treatment bed. On the other hand, volatilization of MBr from the bed surfaces of the two VIF-covered beds were negligible. Volatilization losses occurred from the edges of all the beds covered with PE or VIF and were greater from the high rate-treatment beds. Initial vertical diffusion of MBr in the subsurface of the beds covered with PE or VIF was mainly upward, as large concentrations of MBr were detected from near bed surfaces to 20 cm depth in these beds 30 minutes after injection and little or no MBr was found at 40 cm depth. The two VIF-covered beds exhibited greater MBr concentrations and longer resident times in the root zone (0.5-40 cm depth) than corresponding PE-covered beds. Concentrations of MBr in the root zone of the high rate-treatment beds were 3.6-6.1 times larger than the low rate-treatment beds during the first days after application. In conclusion, VIF promoted retention of MBr in the root zone and, if volatilization loss from bed edges can be blocked, volatilization loss from VIF-covered beds should be negligible.     

Relative effect of soil moisture on emissions and distribution of 1,3-dichloro-propene and chloropicrin in soil columns

Emissions of soil fumigants are regulated to protect air quality in California. Irrigation prior to fumigation can reduce fumigant emissions at relatively low costs; however, the optimum range of soil water content that reduces emissions without reducing efficacy is not clearly defined. The objective of this study was to determine the effects of soil water content [at 30, 45, 60, 75, 90 and 100% field capacity (FC)] on the emission and distribution of fumigants 1,3-dichloropropene (1,3-D) and chloropicrin (CP) in columns packed with a sandy loam soil. After injecting equal amounts of cis-1,3-D, trans-1,3-D, and CP, fumigant emissions and distribution in soil were monitored for 14 days. Emissions of all three compounds showed similar response to soil water content except that CP emissions were lower than both isomers of 1,3-D. The emission peak flux was highest and occurred earliest in the driest soil while it was reduced and delayed as soil water content increased. After the peak, emission flux decreased rapidly in the driest soil but more slowly in higher water content treatments. Initially, higher soil water content resulted in substantially lower cumulative emissions among the treatments, but as time progressed, the differences in cumulative emissions decreased or even disappeared. These trends were likely due to the effect of the closed-bottom short soil columns which allowed fumigants to only move upward and contribute to emission. Higher fumigant concentrations in the soil–gas phase were observed in high soil water content treatments, due to less emission loss and more fumigant retained in the soil.     

Emission, distribution and leaching of methyl isothiocyanate and chloropicrin under different surface containments

The environmental fate of fumigants methyl isothiocyanate (MITC) and chloropicrin (CP) is of great concern for potential air and groundwater contamination while retaining sufficient concentrations for pest control efficacy. The emission, gas phase distribution, leaching, and persistence of MITC and CP were examined in repacked columns filled with sandy soils under three surface conditions: tarp without irrigation, tarp with limited irrigation, and 5-d irrigation without tarp cover. For MITC, cumulative emission constituted 62%, 36%, and 0.3% of the amount applied under tarp without irrigation, tarp with limited irrigation, and 5-d irrigation without tarp surface conditions, respectively. The corresponding cumulative emission losses were 45%, 30%, and 5.4% for CP. During the first 24h after injection, soil air concentrations of the two fumigants were much higher in the 15-25cm depth range than other depths in the soil profile. Small amounts of leaching occurred for both fumigants, indicating potential for groundwater contamination should heavy rain fall or irrigation occurs immediately after soil fumigation. Very small amounts of residual MITC and CP (<2%) were found in the soil 24 days after the experiment. The study clearly showed that atmospheric emission and degradation were the two primary pathways of MITC and CP dissipation during soil fumigation. Emission could be effectively reduced with 5-d irrigation if small leaching is acceptable or be prevented.     

Effect of plastic tarps over raised-beds and potassium thiosulfate in furrows on chloropicrin emissions from drip fumigated fields

Plastic tarps are commonly used in raised bed strawberry production to minimize emissions of preplant soil fumigants and are left in place throughout the growing season as part of the standard cultural practices. Soil amendments with chemicals such as thiosulfate (S2O3(2-)) can reduce fumigant emissions. A field study was conducted near Santa Maria, CA to determine the effects of low density polyethylene (LDPE) and virtually impermeable film (VIF) over raised-beds and applying potassium thiosulfate (KTS) in furrows on reducing chloropicrin (CP) emissions from a strawberry field. Four fields (or treatments) were tested with 224 kg ha(-1) CP drip-applied threecm under the soil surface. The CP flux from bed tops and furrows and gas-phase concentrations under the tarps were monitored for five d. The CP emission flux and concentration under tarp were highest immediately following application. Diurnal temperature change affected CP concentration and emission fluxes (higher values during the day and lower at night). Slightly higher CP cumulative emission occurred using LDPE tarp (19%) compared to VIF (17%). Normalized flux (CP emission flux from the beds divided by CP concentration under the tarp) being estimated from field measurement was slightly higher for LDPE than VIF indicating different tarp permeability in the field. Because of extremely low emissions from the furrows (<0.2% of total emission loss), KTS application to furrow treatments did not show further emission reductions than non-KTS treatments. This indicates that emission reduction should focus on the tarp above raised-beds when fumigant was drip-applied near bed-surface.     

Long-term dynamics of the atrazine mineralization potential in surface and subsurface soil in an agricultural field as a response to atrazine applications

The dynamics of the atrazine mineralization potential in agricultural soil was studied in two soil layers (topsoil and at 35-45 cm depth) in a 3 years field trial to examine the long term response of atrazine mineralizing soil populations to atrazine application and intermittent periods without atrazine and the effect of manure treatment on those processes. In topsoil samples, ¹⁴C-atrazine mineralization lag times decreased after atrazine application and increased with increasing time after atrazine application, suggesting that atrazine application resulted into the proliferation of atrazine mineralizing microbial populations which decayed when atrazine application stopped. Decay rates appeared however much slower than growth rates. Atrazine application also resulted into the increase of the atrazine mineralization potential in deeper layers which was explained by the growth on leached atrazine as measured in soil leachates recovered from that depth. However, no decay was observed during intermittent periods without atrazine application in the deeper soil layer. atzA and trzN gene quantification confirmed partly the growth and decay of the atrazine degrading populations in the soil and suggested that especially trzN bearing populations are the dominant atrazine degrading populations in both topsoil and deeper soil. Manure treatment only improved the atrazine mineralization rate in deeper soil layers. Our results point to the importance of the atrazine application history on a field and suggests that the long term survival of atrazine degrading populations after atrazine application enables them to rapidly proliferate once atrazine is again applied.     

Comparison of the occurrence of antibiotics in four full-scale wastewater treatment plants with varying designs and operations

The occurrence of ciprofloxacin, sulfamethoxazole, tetracycline, and trimethoprim antibiotics in four full-scale wastewater treatment plants (WWTPs) that differ in design and operating conditions was determined. The WWTPs chosen utilized a variety of secondary removal processes, such as a two stage activated sludge process with a nitrification tank, extended aeration, rotating biological contactors, and pure oxygen activated sludge. Several of the WWTPs also employed an advanced treatment process, such as chlorination and UV radiation disinfection. The detected concentrations (microg/l) ranged from 0.20 to 1.4 for ciprofloxacin, 0.21 to 2.8 for sulfamethoxazole, 0.061 to 1.1 for tetracycline, and 0.21 to 7.9 for trimethoprim. The overall percent difference in the concentrations of the antibiotics in the effluent and influent of these antibiotics differed between plants and ranged from 33% to 97%. Based on these four full-scale WWTPs evaluated, the apparent removal of organic micropollutants in wastewater is dependent on a combination of biological and physico-chemical treatment processes and operating conditions of the treatment system.     

Sorption of atrazine and metolachlor by burrow linings developed in soils with different crop residues at the surface

Atrazine and metolachlor sorption by earthworm (Lumbricus terrestris L.) burrows was measured by introducing herbicides into the burrows and collecting the effluent between 0 to 3, 3 to 6, and 6 to 9 min of simulated burrow flow. On average, sorption by burrow linings reduced the herbicide concentration to 78% (atrazine) and 74% (metolachlor) of the applied herbicide solution concentration. For both herbicides, the amount sorbed was dependent on the food source available to the earthworm, as well as the duration of burrow flow. On average, soybean-fed- and corn-fed-earthworm-burrows significantly retained more herbicides relative to the Control Treatment (unfed-earthworms). More herbicides were transported through the burrows with time because the lateral flow movement from the burrow wall into the soil matrix decreased. It is also likely that herbicides retained on burrow linings during the first 3 min of flow saturated the adsorption sites on the burrow wall, which decreased the subsequent retention potential of herbicides in flow between 3 to 9 min. Based on these results, we conclude that herbicide transport through earthworm burrows in the field will be related to crop and crop residue management practices.     

Comparison of the method of diffusive gels in thin films with conventional extraction techniques for evaluating zinc accumulation in plants and isopods

The measurement of diffusive gels in thin films (DGT) has recently been developed to assess metal bioavailability in soils. The DGT-method is based on diffusion in a porous matrix. To test the predictive capabilities of the method with regard to metal bioavailability, a study was set up with 28 soils having a variety of textures and amounts of zinc salts added. Correlation and regression analyses were performed to compare DGT-extracted zinc levels to zinc concentrations obtained by extraction with 0.01 M CaCl(2) and 0.43 M HNO(3), digestion with aqua regia and the zinc concentration in pore water. The amount of zinc extracted with CaCl(2) correlated well with DGT-extracted zinc levels in all soils spiked with different amounts of ZnCl(2). A similar correlation was not found for zinc concentrations in soil samples collected in the field. Experiments were performed to compare zinc content in organisms and in soils. The organisms tested were plants (grass, lettuce and lupine) and the hard bodied soil dwelling isopod Oniscus asellus. Good correlations were found between zinc accumulation in grass and lettuce and the C(E) (effective concentration) measured by a DGT-device, CaCl(2) extracted zinc and the zinc content in the pore water of all soils. The correlation with C(E) was not significant for lupine, neither for spiked soils, nor for field soils (p< or =0.001). Zinc levels in the isopods were not significantly related to any set of zinc measurements. From a synthesis of all results obtained it is concluded that the DGT-methodology does not have an additional value in predicting bioavailability of zinc in terrestrial ecosystems as compared to conventional extraction methods.     

Occurrence and distribution of selected pharmaceuticals and personal care products in aquatic environments: a comparative study of regions in China with different urbanization levels

Purpose

We analyzed and compared the distributions of 13 target pharmaceuticals in different water samples from the Hangzhou metropolitan area and Linan County, Southeast China.

Methods

Sampling was conducted in five hospitals, two wastewater treatment plants (WWTPs), and Qiantang River. Samples were concentrated by solid-phase extraction and PPCP concentrations were determined by UPLC-MS/MS.

Results and discussion

Trimethoprim, erythromycin A dihydrate, norfloxacin, ofloxacin, diclofenac sodium, and atenolol were the most frequently detected pharmaceuticals in hospital effluents. Most of the pharmaceutical concentrations in hospital effluents were higher than those in the WWTP influents. Although both WWTPs adopt the anaerobic?Caerobic?Canoxic treatment process, the removal rates for pharmaceuticals, such as trimethoprim and diclofenac sodium, were completely different. Meanwhile, erythromycin A dihydrate, ofloxacin, penicillin-G, cephalexin, cefazolin, ibuprofen, and diclofenac sodium were detected in Qiantang River.

Conclusions

These results indicate that hospitals are more concentrated sources of pharmaceuticals than WWTPs, and the WWTPs are not the only route of entry of pharmaceuticals into aquatic environments in these two regions.