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.     

Effects of biochar on the emissions,soil distribution,and nematode control of 1,3-dichloropropene

Emissions of volatile soil fumigant 1,3-dichloropropene (1,3-D) from soil to air are a significant concern in relation to air quality, and cost-effective strategies to reduce such emissions are urgently required by growers to help them comply with increasingly stringent regulations. In this work, application of a rice husk-derived biochar to the surface of a sandy loam soil chamber reduced soil–air emissions of 1,3-D from 42% in a control (no biochar) to 8% due to adsorption onto the biochar. This adsorbed 1,3-D showed a potential for re-volatilization into air and solubilization into the soil–liquid phase. Biochar at the soil surface also reduced soil–gas concentrations in the upper soil; based on the determination of concentration–time values, this may limit 1,3-D-induced nematode control in the upper soil. In batch studies, the mixing of biochar into the soil severely limited nematode control; 1,3-D application rates around four times greater than the maximum permissible limit would be required to give nematode control under such conditions. Therefore, the use of biochar as a surface amendment, while showing an emission reduction benefit, may limit pest control during subsequent fumigations if, as seems probable, it is plowed into 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.     

Atmospheric volatilization of methyl bromide, 1,3-dichloropropene,and propargyl bromide through two plastic films: transfer coefficient and temperature effect

Atmospheric emission of methyl bromide (MeBr) and its potential alternative chemicals such as 1,3-dichloropropene (1,3-D) and propargyl bromide (PrBr) can contribute to air pollution and ozone depletion (for MeBr). One of the main sources of these chemicals is from agricultural soil fumigation. To understand the volatilization dynamics, emission of MeBr, 1,3-D, and PrBr through a polyethylene-based high-barrier film (HBF) and a virtually impermeable film (VIF) was measured using an air flow and sampling system that produced >90% mass balance. The experiment was conducted outdoors and was subjected to ambient daily temperature variations. The HBF film was found to be very permeable to 1,3-D and PrBr, but somewhat less permeable to MeBr. The VIF film was very impermeable to 1,3-D, PrBr, or MeBr. Measured volatilization flux, in general, exhibited strong diurnal variations which were controlled by film temperature. Unlike the HBF film, a time lag (∼12 h) was observed between high-temperatures and high-emission flux values for the VIF film. An impermeable film may be used as an effective means of controlling the atmospheric emission of MeBr and its alternative chemicals.     

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 modeling with empirical calculation of diffuse and fugitive methane emissions in a Spanish landfill

One of the most significant environmental problems arising from landfills is the emission of methane into the atmosphere. In this study, methane emissions from a currently in-use Spanish landfill were modeled as well as being experimentally measured using a two-step method. The first step involved a qualitative walkover survey to detect where gases were being emitted on the surface of the landfill. The second stage comprised a quantitative analysis of these surface methane emissions at a selected number of points on the landfill surface using a specially designed flux chamber. The statistical analysis of the data obtained was based on the Sichel function and resulted in an average emission rate of 74.9 g·m^?2·day^?1, with 27.8 and 202.1 g·m^?2·day^?1 as the lower and upper limits of the 95% confidence interval, respectively. The total emission for the landfill, with an emitting surface of 335,000 m², is 9.16 × 10³ ton/yr. These values have been compared with those from three different models, with the model results being above the calculated mean emissions measured at the landfill, but below the upper confidence limit at 95%.

Implications: One of the main environmental problems arising from the presence of landfills is the emission of biogas (which mainly contains methane and carbon dioxide) into the atmosphere. Several experimental methods as well as models have been developed to quantify these emissions. In this work, the authors have compared the results obtained using experimental measurements with those provided by some local and international models using the default parameters proposed. The results obtained from the experimental method are in accordance with those provided by the models, although the models could be slightly overestimating these emissions.     

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.     

Comparison of measured and modeled surface ozone concentrations at two different sites in Europe during the solar eclipse on August 11, 1999

The effects of the solar eclipse on 11 August 1999 on surface ozone at two sites, Thessaloniki, Greece (urban site) and Hohenpeissenberg, Germany (elevated rural site) are investigated in this study and compared with model results. The eclipse offered a unique opportunity to test our understanding of tropospheric ozone chemistry and to investigate with a simple photochemical box model the response of surface ozone to changes of solar radiation during a photolytical perturbation such as the solar eclipse. The surface ozone measurements following the eclipse display a decrease of around 10–15 ppbv at the urban station of Eptapyrgio at Thessaloniki while at Hohenpeissenberg, the actual ozone data do not show any clear effect of eclipse on surface ozone. For Thessaloniki, the model results suggest that solely photochemistry can account for a significant amount of the observed surface ozone decrease during the eclipse but transport effects mask part of the photochemical effect of eclipse on surface ozone. For Hohenpeissenberg, the box model predicted an ozone decrease, due to the eclipse, of about 2 ppbv in relative agreement with the magnitude of the observed ozone decrease from the 2 h moving average while at the same time it inhibits the foreseen diurnal ozone increase. However, this modeled ozone decrease during the eclipse is small compared to the diurnal ozone variability due to transport effects, and hence, transport really masks such relative small changes. The different magnitude of the surface ozone decrease between the two sites indicates mainly the role of the NO_x levels. Measured and modeled NO and NO₂ concentrations at Hohenpeissenberg during the eclipse are also compared and indicate that the partitioning of NO and NO₂ in NO_x is influenced clearly from the eclipse. This is not observed at Thessaloniki due to local NO_x sources.     

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.     

太湖不同营养类型湖区沉积物磷的形态与吸附行为的比较

选择太湖不同营养类型的湖区开展了沉积物磷形态与磷吸附行为的研究,结果表明,位于藻型湖区梅梁湾的T1点表层沉积物中的总磷(TP)含量高于位于草型湖区T2点的相应值,且沉积物吸附能(K)值与TP含量显著负相关(ppp0)值随深度递增,大型水生植物的存在促使表层沉积物维持磷汇的功能,T1点沉积物距表层10~15cm处EPC0值最低,故相应疏浚深度宜为10~15cm,这一结果为富营养化湖泊的修复提供了理论依据与技术参数。     

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.