Biodegradation of α and β Endosulfan in Soil as Influenced by Application of Different Organic Materials

Abstract

A laboratory pot experiment was conducted to study the effect of amending soil with four different sources of organic matter on the degradation rate of α and β endosulfan isomers. Poultry by-product meal, poultry manure, dairy manure, and municipal solid waste compost were cured, dried, ground (<1 mm) and thoroughly mixed with a calcareous soil at a rate of 2% and placed in plastic pots. Endosulfan was added at the rate of 20 mg kg^?1. The moisture level was kept near field capacity and the pots were kept at room temperature. Soil sub-samples, 100 g each, were collected from every pot at days 1, 8, 15, 22, 29, 43, and 57 for the measurement of endosulfan isomers. Endosulfan residues were extracted from the soil samples with acetone. The supernatant was filtered through anhydrous sodium sulphate, 5 mL aliquot was diluted to 25 mL with hexane, mixed well, and then two sub-samples from the filtrates were analyzed for α and β endosulfan isomers by gas chromatography. The results indicated that the half-life (T _½) of α-endosulfan in the poultry by-product meal treatment was 15 days compared to about 22 days in the other treatments. The T _½ of β-endosulfan was 22 days in the poultry by-product meal treatment and followed a bi-phasic pattern, 57 days in the municipal solid waste compost treatment and the extrapolated T _½ was about 115 days for the other three treatments.     

Method Development for Determination of Fluroxypyr in Soil

Abstract

Four methods were developed for the analysis of fluroxypyr in soil samples from oil palm plantations. The first method involved the extraction of the herbicide with 0.05 M NaOH in methanol followed by purification using acid base partition. The concentrated material was subjected to derivatization and then cleaning process using a florisil column and finally analyzed by gas chromatography (GC) equipped with electron capture detector (ECD). By this method, the recovery of fluroxypyr from the spiked soil ranged from 70 to 104% with the minimum detection limit at 5 µg/kg. The second method involved solid liquid extraction of fluroxypyr using a horizontal shaker followed by quantification using high performance liquid chromatography (HPLC) equipped with UV detector. The recovery of fluroxypyr using this method, ranged from 80 to 120% when the soil was spiked with fluroxypyr at 0.1–0.2 µg/g soil. In the third method, the recovery of fluroxypyr was determined by solid liquid extraction using an ultrasonic bath. The recovery of fluroxypyr at spiking levels of 4–50 µg/L ranged from 88 to 98% with relative standard deviations of 3.0–5.8% with a minimum detection limit of 4 µg/kg. In the fourth method, fluroxypyr was extracted using the solid liquid extraction method followed by the cleaning up step with OASIS® HLB (polyvinyl dibenzene). The recovery of fluroxypyr was between 91 and 95% with relative standard deviations of 4.2–6.2%, respectively. The limit of detection in method 4 was further improved to 1 µg/kg. When the weight of soil used was increased 4 fold, the recovery of fluroxypyr at spiking level of 1–50 µg/kg ranged from 82–107% with relative standard deviations of 0.5–4.7%.     

Use of Composted Animal Manures to Reduce 1,3-Dichloropropene Emissions

Atmospheric emission of the soil fumigant 1,3-dichloropropene (1,3-D) has been associated with the deterioration of air quality in certain fumigation areas. To minimize the environmental impacts of 1,3-D, feasible and cost-effective control strategies are in need of investigation. One approach to reduce emissions is to enhance the surface layer of a soil to degrade 1,3-D. A field study was conducted to determine the effectiveness of composted steer manure (SM) and composted chicken manure (CKM) to reduce 1,3-D emissions. SM or CKM were applied to the top 5-cm soil layer at a rate of 3.3 or 6.5 kg m^?2. An emulsified formulation of 1,3-D was applied through drip tape at 130.6 kg ha^?1 into raised beds. The drip tape was placed in the center of each bed (102 cm wide) and 15 cm below the surface. Passive flux chambers were used to measure the loss of 1,3-D for 170 h after fumigant application. Results indicated that the cumulative loss of 1,3-D was about 48% and 28% lower in SM- and CKM-amended beds, respectively, than in the unamended beds. Overall, both isomers of 1,3-D behaved similarly in all treatments. The cumulative loss of 1,3-D, however, was not significantly different between the two manure application rates for either SM or CKM. The results of this study demonstrate the feasibility of using composted animal manures to control 1,3-D emissions.     

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.     

Effects of Soil Amendments at a Heavy Loading Rate Associated with Cover Crops as Green Manures on the Leaching of Nutrients and Heavy Metals from a Calcareous Soil

The potential risk of groundwater contamination by the excessive leaching of N, P and heavy metals from soils amended at heavy loading rates of biosolids, coal ash, N‐viro soil (1:1 mixture of coal ash and biosolids), yard waste compost and co‐compost (3:7 mixture of biosolids to yard wastes), and by soil incorporation of green manures of sunn hemp (Crotalaria juncea) and sorghum sudangrass (Sorghum bicolor × S. bicolor var. sudanense) was studied by collecting and analyzing leachates from pots of Krome very gravelly loam soil subjected to these treatments. The control consisted of Krome soil without any amendment. The loading rate was 205 g pot^? 1 for each amendment (equivalent to 50 t ha^? 1 of the dry weight), and the amounts of the cover crops incorporated into the soil in the pot were those that had been grown in it. A subtropical vegetable crop, okra (Abelmoschus esculentus L.), was grown after the soil amendments or cover crops had been incorporated into the soil. The results showed that the concentration of NO₃‐N in leachate from biosolids was significantly higher than in leachate from other treatments. The levels of heavy metals found in the leachates from all amended soils were so low, as to suggest these amendments may be used without risk of leaching dangerous amounts of these toxic elements. Nevertheless the level of heavy metals in leachate from coal ash amended soil was substantially greater than in leachates from the other treatments. The leguminous cover crop, sunn hemp, returned into the soil, increased the leachate NO₃‐N and inorganic P concentration significantly compared with the non‐legume, sorghum sudangrass. The results suggest that at heavy loading rates of soil amendments, leaching of NO₃ ^? could be a significant concern by application of biosolids. Leaching of inorganic P can be increased significantly by both co‐compost and biosolids, but decreased by coal ash and N‐viro soil by virtue of improved adsorption. The leguminous cover crop, sunn hemp, when incorporated into the soil, can cause the concentration of NO₃‐N to increase by about 7 fold, and that of inorganic P by about 23% over the non‐legume. Regarding the metals, biosolids, N‐viro soil and coal ash significantly increased Ca and Mg concentrations in leachates. Copper concentration in leachate was increased by application of biosolids, while Fe concentration in leachates was increased by biosolids, coal ash and co‐compost. The concentrations of Zn, Mo and Co in leachate were increased by application of coal ash. The concentrations of heavy metals in leachates were very low and unlikely to be harmful, although they were increased significantly by coal ash application.     

INFLUENCE OF SOIL ORGANIC MATTER ON THE LEACHING OF POLYCYCLIC AROMATIC HYDROCARBONS IN SOIL

Polycyclic aromatic hydrocarbons (PAHs) are one of the main classes of contaminants in the terrestrial environment. Aside from total organic carbon, the ratio among the different organic matter fractions [dissolved organic matter, fulvic acid (FA), humic acid (HA) and humin] can also affect the mobility of these hydrocarbons in soils. In this study the effect of the whole organic carbon pool has been compared with that of HA and FA on the translocation of four PAHs (biphenyl, fluorene, phenanthrene and pyrene) in soil columns. Oxidized and untreated soil columns with and without HA or FA, were prepared, spilled with hydrocarbons and leached with a 0.01 M CaCl₂ solution. The influence of HA and FA on PAH translocation was investigated through determinations of the PAH contents and total organic carbon (TOC) in the layers of the columns. All molecules were moved vertically by the percolating solutions, their concentrations decreasing with depths. The non-oxidized soil tended to retain more PAHs (96%) than the oxidized one (60%), confirming that organic matter plays an important role in controlling PAH leaching. The whole organic matter pool reduced the translocation of pollutants downward the profile. The addition of HA enhanced this behaviour, by increasing the PAH retention in the top layers (7.55 mg and 4.00 mg in the top two layers, respectively) while FA increased their mobility (only 2.30 and 2.90 mg of PAHs were found in the top layers) and favoured leaching. In fact, in the presence of HA alone, the higher amounts of PAHs retained at the surface and the good correlation (r²=0.936) between TOC and hydrocarbon distribution can be attributed to a parallel distribution of PAHs and HA, while in the presence of FA, the higher mobility of PAHs can be attributed to the high mobility of the humic material, as expected by its extensive hydrophilic characteristics.     

Matrix effect on the performance of headspace solid phase microextraction method for the analysis of target volatile organic compounds (VOCs) in environmental samples

Solid phase microextraction (SPME) is a fast, cheap and solvent free methodology widely used for environmental analysis. A SPME methodology has been optimized for the analysis of VOCs in a range of matrices covering different soils of varying textures, organic matrices from manures and composts from different origins, and biochars. The performance of the technique was compared for the different matrices spiked with a multicomponent VOC mixture, selected to cover different VOC groups of environmental relevance (ketone, terpene, alcohol, aliphatic hydrocarbons and alkylbenzenes). VOC recovery was dependent on the nature itself of the VOC and the matrix characteristics. The SPME analysis of non-polar compounds, such as alkylbenzenes, terpenes and aliphatic hydrocarbons, was markedly affected by the type of matrix as a consequence of the competition for the adsorption sites in the SPME fiber. These non-polar compounds were strongly retained in the biochar surfaces limiting the use of SPME for this type of matrices. However, this adsorption capacity was not evident when biochar had undergone a weathering/aging process through composting. Polar compounds (alcohol and ketone) showed a similar behavior in all matrices, as a consequence of the hydrophilic characteristics, affected by water content in the matrix. SPME showed a good performance for soils and organic matrices especially for non-polar compounds, achieving a limit of detection (LD) and limit of quantification (LQ) of 0.02 and 0.03 ng g⁻¹ for non-polar compounds and poor extraction for more hydrophilic and polar compounds (LD and LQ higher 310 and 490 ng g⁻¹). The characteristics of the matrix, especially pH and organic matter, had a marked impact on SPME, due to the competition of the analytes for active sites in the fiber, but VOC biodegradation should not be discarded in matrices with active microbial biomass.     

An Evaluation of the Effects of Soil Characteristics on Mitigation and Restoration Involving Blue Elderberry, <Emphasis Type="Italic">Sambucus mexicana</Emphasis>

We conducted field surveys and laboratory analyses to test the effects of soil characteristics in habitat mitigation sites and natural sites on the growth and condition of blue elderberry (Sambucus mexicana), which is the sole host plant for the federally threatened Valley elderberry longhorn beetle (Desmocerus californicus dimorphus). Thirty mitigation and 16 natural sites were selected throughout the range of the beetle. We found that although plant relative growth rates were comparable between mitigation sites and a natural site, mitigation sites contained substantially less soil nutrients than mitigation sites. Within mitigation sites, elderberry health and growth were positively correlated with the amount of total nitrogen in soils and less strongly with other soil nutrients and soil moisture. Analyses demonstrated reductions in the relative growth rate of elderberry as mitigation sites aged, and that soil nutrients and soil moisture became depleted over time. For mitigation sites, it took approximately seven years to develop basal stem diameters that have been linked to successful beetle colonization. Mitigation sites have smaller shrubs than natural sites and growth slows as mitigation sites age, thus delaying convergence of conditions between natural and mitigation sites. Analyses of soil particle size and whether sites were within the 100-year floodplain (as an indicator of riparian conditions) were inconclusive. We recommend investigating fertilizing and optimum planting densities for elderberry at restoration and mitigation sites, as well as increasing the duration of irrigation and monitoring.     

Determinants of Farmers’ Adoption of Improved Soil Conservation Technology in a Middle Mountain Watershed of Central Nepal

This study explores different socio-economic and institutional factors influencing the adoption of improved soil conservation technology (ISCT) on Bari land (Rainfed outward sloping terraces) in the Middle Mountain region of Central Nepal. Structured questionnaire survey and focus group discussion methods were applied to collect the necessary information from farm households. The logistic regression model predicted seven factors influencing the adoption of improved soil conservation technology in the study area including years of schooling of the household head, caste of the respondent, land holding size of the Bari land, cash crop vegetable farming, family member occupation in off farm sector, membership of the Conservation and Development Groups, and use of credit. The study showed that technology dissemination through multi-sectoral type community based local groups is a good option to enhance the adoption of improved soil conservation technology in the Middle Mountain farming systems in Nepal. Planners and policy makers should formulate appropriate policies and programs considering the farmers' interest, capacity, and limitation in promoting improved soil conservation technology for greater acceptance and adoption by the farmers.     

Fate of imidacloprid in soil and plant after application to cotton seeds

This study aimed to investigate the persistence of imidacloprid in soil after application to cotton seeds and to obtain a complete picture on the mass balance of this compound in soil and cotton plants. The study was carried out as a pot culture experiment under laboratory conditions using a Gaucho formulation containing ¹⁴C-labeled imidacloprid. Three treatments of cotton seeds were made in sandy loamy soil: live seeds grown in autoclaved soil, dead seeds put in live soil and live seeds grown in live soil. Results showed that total ¹⁴C recoveries decreased by time ranging 93.8–96.2, 77.1–88.4 and 53.5–62.4% of the applied radioactivity at 7, 14, and 21 d after application, respectively. The reduction in the extracted ¹⁴C from soil coincided with the increase of non-extracted ones. Levels of bound ¹⁴C was always less in autoclaved soil than in live ones. Results revealed also that only 1.8–6.8% of the applied ¹⁴C was taken up by the plants and fluctuated within the test period. ¹⁴C levels were higher in plants grown in autoclaved soil than those in live ones and the radioactivity tended to accumulate on the edges of cotton leaves. Most of the radioactivity in the soil extracts was identified as unchanged ¹⁴C-imidacloprid.