Ecotoxicological assessment of doxycycline in soil

Doxycycline has been used in continually increasing quantities for mass treatment of food animals because of its greater bioavailability relative to older tetracyclines. The study presented in this paper was undertaken to investigate the degradation rate of the tetracycline derivative in manure-amended soil. In the present experiment, following composting, the doxycycline-contaminated manure was applied to agricultural land, and a field study was performed to investigate the degradation rate of doxycycline in soil. By the end of the 20-week sampling period, about 20 %, 33 % and 18 % of the initial doxycycline concentrations could be measured in soil samples taken at three different soil depths. The calculated half-life of doxycycline in the soil was 66.5, 76.3 and 59.4 days at depths of 0 cm, 25 cm and 50 cm, respectively. The potential effect of doxycycline on soil microbial activity was demonstrated by the nitrogen transformation test performed in compliance with the Organisation for Economic Co-operation and Development (OECD) Guideline No. 216. On day 28, the following nitrate concentrations of the control soil sample were found in the soil samples treated with different amounts of doxycycline: 76.9 %, 53.0 %, 65.6 %, 59.7 % and 77.1 %.     

Microbial aspects of the interaction between soil depth and biodegradation of the herbicide isoproturon

Factors controlling change in biodegradation rate of the pesticide isoproturon with soil depth were investigated in a field with sandy-loam soil. Soil was sampled at five depths between 0-10 and 70-80 cm. Degradation rate declined progressively down the soil profile, with degradation slower, and relative differences in degradation rate between soil depths greater, in intact cores relative to sieved soil. Neither the maximum rate of degradation, or sorption, changed with soil depth, indicating that there was no variation in bioavailability. Differences in degradation rate between soil depths were not associated with the starting population size of catabolic organisms or the number of catabolic organisms proliferating following 100% degradation. Decreasing degradation rates with soil depth were associated with an increase in the length of the lag phase prior to exponential degradation, suggesting the time required for adaptation within communities controlled degradation rates. 16S rRNA PCR denaturing gradient gel electrophoresis showed that degradation in sub-soil between 40-50 and 70-80 cm depths was associated with proliferation of the same strains of Sphingomonas spp.     

Study of the spatial variation of the biodegradation rate of the herbicide bentazone with soil depth using contrasting incubation methods

Vertical and horizontal spatial variability in the biodegradation of the herbicide bentazone was compared in sandy-loam soil from an agricultural field using sieved soil and intact soil cores. An initial experiment compared degradation at five depths between 0 and 80 cm using sieved soil. Degradation was shown to follow the first-order kinetics, and time to 50% degradation (DT(50)), declined progressively with soil depth from 56 d at 0-10 cm to 520 d at 70-80 cm. DT(50) was significantly correlated with organic matter, pH and dehydrogenase activity. In a subsequent experiment, degradation rate was compared after 127 d in sieved soil and intact cores from 0 to 10 and 50 to 60 cm depth from 10 locations across a 160x90 m portion of the field. Method of incubation significantly affected mean dissipation rate, although there were relatively small differences in the amount of pesticide remaining in intact cores and sieved soil, accounting for between 4.6% and 10.6% of that added. Spatial variability in degradation rate was higher in soil from 0 to 10 cm depth relative to that from 50 and 60 cm depth in both sieved soil and intact core assessments. Patterns of spatial variability measured using cores and sieved soil were similar at 50-60 cm, but not at 0-10 cm depth. This could reflect loss of environmental context following processing of sieved soil. In particular, moisture content, which was controlled in sieved soil, was found to be variable in cores, and was significantly correlated with degradation rate in intact topsoil cores from 0 to 10 cm depth.     

Influence of the DMPP (3,4-dimethyl pyrazole phosphate) on nitrogen transformation and leaching in multi-layer soil columns

The application of nitrogen fertilizers leads to various ecological problems such as nitrate leaching. The use of nitrification inhibitors as nitrate leaching retardants is a proposal that has been suggested for inclusion in regulations in many countries. In this study, using a multi-layer soil column device, the influence of new nitrification inhibitor DMPP (3,4-dimethyl pyrazole phosphate) was studied for understanding the nitrogen vertical transformation and lowering the nitrate leaching at different soil profile depths. The results indicated that, within 60 d of experiment, the regular urea added 1.0% DMPP can effectively inhibit the ammonium oxidation in the soil, and improve the ammonium concentration in soil solution over the 20cm depths of soil profile, while decline the concentrations of nitrate and nitrite. No obvious difference was found on ammonium concentrations in soil solution collected from deep profile under 20cm depths between regular urea and the urea added 1.0% DMPP. There was also no significant difference for the nitrate, ammonium and nitrite concentrations in the soil solution under 40cm depths of soil profile with the increasing nitrogen application level, among the treatments of urea added 1.0% DMPP within 60 d. It is proposed that DMPP could be used as an effective nitrification inhibitor in some region to control ammonium oxidation and decline the ion-nitrogen leaching, minimizing the shallow groundwater pollution risk and being beneficial for the ecological environment.     

Leaching and half-life of the herbicide tebuthiuron on a recharge area of Guarany aquifer in sugarcane fields in Brazil

This study was undertaken to evaluate the degradation and mobility of the herbicide tebuthiuron (N-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl]-N,N'-dimethylurea) in soil under field conditions, and its potential for leaching and groundwater contamination. A watershed, Espraiado, located over a recharge area in Brazil, was chosen for soil and water studies. At Espraiado, water samples were collected from seven wells at intervals of three months from March 2004 to June 2006 and analyzed for tebuthiuron. Other samples were taken from city wells located outside of the recharge area. To assess the potential movement to the aquifer, tebuthiuron was also applied to trial plots at the recommended label rate of 1.0 kg/ha a.i. in May of 2004, with and without sugarcane coverage, on sandy soil. Soil samples were collected during the years of 2004 and 2005, at depths intervals of 20 cm from soil surface down to 120 cm and analyzed for tebuthiuron at zero, 3, 30, 60, 90, 120, 150, 180, 240, and 300 days after application. There was no clear effect of sugarcane coverage on the tebuthiuron degradation in soils, but it moved faster into the soil where there was no cover. After 180 days there were no measurable residues in the soil, and tebuthiuron was not found below 40 cm depth in any time. Tebuthiuron had a half-life of 20 days under those conditions. No tebuthiuron residue was found in ground water samples at any sampling time.     

Leaching and half-life of the herbicide tebuthiuron on a recharge area of Guarany aquifer in sugarcane fields in Brazil

This study was undertaken to evaluate the degradation and mobility of the herbicide tebuthiuron (N-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl]-N,N′-dimethylurea) in soil under field conditions, and its potential for leaching and groundwater contamination. A watershed, Espraiado, located over a recharge area in Brazil, was chosen for soil and water studies. At Espraiado, water samples were collected from seven wells at intervals of three months from March 2004 to June 2006 and analyzed for tebuthiuron. Other samples were taken from city wells located outside of the recharge area. To assess the potential movement to the aquifer, tebuthiuron was also applied to trial plots at the recommended label rate of 1.0 kg/ha a.i. in May of 2004, with and without sugarcane coverage, on sandy soil. Soil samples were collected during the years of 2004 and 2005, at depths intervals of 20 cm from soil surface down to 120 cm and analyzed for tebuthiuron at zero, 3, 30, 60, 90, 120, 150, 180, 240, and 300 days after application. There was no clear effect of sugarcane coverage on the tebuthiuron degradation in soils, but it moved faster into the soil where there was no cover. After 180 days there were no measurable residues in the soil, and tebuthiuron was not found below 40 cm depth in any time. Tebuthiuron had a half-life of 20 days under those conditions. No tebuthiuron residue was found in ground water samples at any sampling time.     

Mineralisation studies of 14C-labelled metsulfuron-methyl, tribenuron-methyl, chlorsulfuron and thifensulfuron-methyl in one Danish soil and groundwater sediment profile.

Bacterial mineralisation of four sulfonylurea herbicides at 20 microg kg(-1) in a sandy soil from nine different depths in a sandy soil horizon (5-780 cm) was investigated in laboratory studies. Metsulfuron-methyl, chlorsulfuron, and tribenuron-methyl were 14C-labelled in the sulfonamide ring, while thifensulfuron-methyl was labelled in the thiophene ring. The highest mineralised amount in 126 days was observed for metsulfuron-methyl (40%) followed by tribenuron-methyl (25%), and thifensulfuron-methyl (11%). Chlorsulfuron showed low mineralisation in all the soils tested (<4%). Mineralisation of the herbicides metsulfuron-methyl and tribenuron-methyl varied according to soil depth (upper profile: 5-70 cm, and lower profile: 165-780 cm) and were proven faster in soil taken from depths 5-7 and 30-35 cm, and slower in depths 45-50 and 70-75 cm. Mineralisation was absent in the lower profile (165-780 cm). As an indicator of microbial activity bacterial counts were taken at the experimental start; these counts grouped in three levels: highest in the surface layer (5-7 cm), slightly lower in the depths 30-75 cm, and lowest in the lower profile (165-780 cm). Residual concentrations of metsulfuron-methyl correlated to the accumulated amount mineralised, with high residual concentrations in soil showing low mineralisation. Also chlorsulfuron showed high residual concentrations with increasing depth in the upper profile, but the relatively high dissipation at 30-35 cm and lower one at 45-50 cm could not be related with the lack of mineralisation. This shows that hydrolysis occurs, but mineralisation of the chloro-substituted sulfonamide is restricted. Tribenuron-methyl and thifensulfuron-methyl could not be detected due to interference with other compounds.     

Degradation of silicone polymer in a field soil under natural conditions

Silicone polymers (PDMS = polydimethylsiloxane) are used in numerous consumer and industrial products. Our previous work showed that they will degrade in soil under laboratory conditions. This paper investigates PDMS degradation in the field. Four soil plots (each 2.44 m x 2.44 m) in Michigan were sprayed in May, 1997, with aqueous emulsion to achieve nominal soil PDMS concentrations of 0 (control), 215 (low), 430 (medium), and 860 (high) microg/g. Over the following summer, soil cores (0-5 and 5-10 cm) were collected every two weeks and analyzed for decrease in-total soil PDMS, and decrease in molecular weight of remaining PDMS. PDMS concentrations decreased 50% in 4.5, 5.3, and 9.6 weeks for the low, medium, and high treatments, respectively. Degradation rates were 0.26 (low), 0.44 (medium), and 0.44 (high) g PDMS/m2 day, indicating that degradation capacity of the soil was exceeded by the High treatment. Dimethylsilanediol (DMSD), the main degradation product, was detected in most samples at <5% of original PDMS. This is consistent with laboratory data showing biodegradation and volatilization of DMSD. Deeper sampling (to 20 cm) found only trace amounts of DMSD, and minor downward movement of the polymer. Respraying and subsequent analysis of one plot with a medium treatment in late August showed slow PDMS degradation during the cool, wet fall, followed by a 40% decrease over winter and extensive degradation during the summer of 1998. The study thus shows that PDMS will degrade under field conditions as predicted from laboratory experiments.     

Mercury in soils of three agricultural experimental stations with long-term fertilization in China

Mercury (Hg) in the agricultural ecosystem is a global concern because of its high potential toxicity. The objectives of this study were to determine the concentration and distribution of Hg in soils from three long-term experimental stations, i.e., Taoyuan (TY) and Qiyang (QY) in Hunan Province and Fengqiu (FQ) in Henan Province of China, and thus to assess the possible food and health risk of long-term applications of fertilizers. Soil samples at each site were collected from different fertilization plots and also from soil profiles with depths 0-100 cm. There were significant differences in soil Hg concentrations in 0-20 cm (A) or 20-40 cm (B) horizon among the three experimental stations. QY station showed significantly higher Hg concentrations than TY and FQ stations. However, there were no significant differences in soil Hg concentrations between A and B horizons at each station. It was concluded that the soil Hg concentrations at the three sites were mainly controlled by the parent materials. Moreover, chemical fertilizer, especially phosphorous fertilizers, could influence the soil Hg concentrations to some extent at the station with lower soil Hg concentrations, for example, at TY station. There were minimal amounts of Hg resulting from applications of the other chemical fertilizers and organic manure, and thus the fertilization had very low risk to the food security of the agro-ecosystems in the terms of Hg inputs and contamination.     

Behavior of methyl isothiocyanate in soils under field conditions in Morocco

The behavior of methyl isothiocyanate (MITC), active metabolite of metam-sodium (MS), was studied under field conditions in Morocco. MS was applied through drip irrigation in: (i) uncovered soil, (ii) soil covered with transparent polyethylene, and (iii) soil covered with virtual impermeable film. Concentrations of MITC were determined at different soil depths to determine the distribution of MITC and the concentration-time product (CTP). Six hours after MS application, in a sandy soil, MITC reaches the 20-30 cm soil layer, but remains highly concentrated in the upper 10-20 cm soil layer. In a silty clay soil, MITC was concentrated in the upper 0-10 cm soil layer. The dissipation of MITC under different conditions of application was fast and complete after seven days. However, MITC dissipation time (DT(50)) was <24 h in sandy soil treated, but 63 h in silty clay soil. Under these application conditions of MS, the plastic film reduced MITC loss to the atmosphere but the plastic film quality did not affect the behavior of MITC. The use of plastic film maintained high MITC concentrations and appropriate CTP at different soil depths.     

Mobility of arsenic, cadmium and zinc in a multi-element contaminated soil profile assessed by in-situ soil pore water sampling, column leaching and sequential extraction

Three methods for predicting element mobility in soils have been applied to an iron-rich soil, contaminated with arsenic, cadmium and zinc. Soils were collected from 0 to 30 cm, 30 to 70 cm and 70 to 100 cm depths in the field and soil pore water was collected at different depths from an adjacent 100 cm deep trench. Sequential extraction and a column leaching test in the laboratory were compared to element concentrations in pore water sampled directly from the field. Arsenic showed low extractability, low leachability and occurred at low concentrations in pore water samples. Cadmium and zinc were more labile and present in higher concentrations in pore water, increasing with soil depth. Pore water sampling gave the best indication of short term element mobility when field conditions were taken into account, but further extraction and leaching procedures produced a fuller picture of element dynamics, revealing highly labile Cd deep in the soil profile.     

Degradation of metolachlor in crude extract of Aspergillus flavus

Crude enzyme from a soil fungus, Aspergillus flavus, was isolated from a field soil following repeated applications of metolachlor [2-Chloro-N-(methoxy-1-methylethyl)-2'-ethyl-6'-methyl acetanilide]. Metolachlor hydrolysis by the crude enzyme extract was determined by enzyme assay. The tests were performed in phosphate buffer, pH 7.5, and the reaction was carried out at two herbicide concentrations (20 and 100 microg mL(-1)) and two crude extract volumes (0.2 and 0.5 mL of the homogenized crude extract mixture). The rate of metolachlor degradation was found faster in samples containing higher volume of crude extract, (T(1/2), 5.7 h) for both concentrations of the herbicide. The activities of enzymes responsible for dechlorination coupled with hydroxylation, N-dealkylation, and breaking of amide linkage were found responsible in the degradation.     

Methane oxidation by Dutch grassland and peat soil microflora

The ability of Dutch grassland soil and Dutch peat soil for methane oxidation was investigated. The kinetics of methane oxidation by soil from different depths were determined in batch cultures incubated with 1; 10; 100; and 10,000 ppmv methane, respectively. All 4 applied concentrations of methane were degraded by both types of soil. Thereby, the highest oxidative activities were observed between 5 and 10 cm soil depth. Most importantly, these experiments demonstrated that this soil acts as a sink for methane even at concentrations well below 1 ppmv. Especially at higher methane concentrations (100 - 10,000 ppmv) much higher degradation rates were found in the peat soil. This also correlates with the higher methane production rates which had been observed in peat soil.     

Metals distribution in soils around the cement factory in southern Jordan

Thirty one soil samples were collected from south Jordan around the cement factory in Qadissiya area. The samples were obtained at two depths, 0-10 cm and 10-20 cm and were analyzed by atomic absorption spectrophotometery for Pb, Zn, Cd, Fe, Cu and Cr. Physicochemical factors believed to affect their mobility of metals in soil of the study area were examined such as; pH, TOM, CaCO3, CEC and conductivity. The relatively high concentrations of lead, zinc and cadmium in the soil samples of the investigated area were related to anthropogenic sources such as cement industry, agriculture activities and traffic emissions. It was found that the lead, zinc and cadmium have the highest level in area close to the cement factory, while the concentration of chromium was low. This study indicate that all of the metals are concentrated on the surface soil, and decreased in the lower part of the soil, this due to reflects their mobility and physical properties of soil and its alkaline pH values. The use of factor analysis showed that anthropogenic activities seem to be the responsible source of pollution for metals in urban soils.     

Differential sorption of herbicides as related to soil topography and organic matter 1

Abstract

The sorption of bromacil and simazine by the surface soil (0–15 cm) sampled at various positions along an 8% slope citrus grove (Candler fine sand; Typic Quartzipsamment) and at various depths (0–200 cm) at upper, middle, and lower positions along the slope were investigated. The sorption of both herbicides by the top 15 cm soil decreased considerably from the upper to mid position along the slope and increased at the lower position. The organic matter content and concentrations of Ca, Mg, K, P, and Cu in the soil showed evidence of transport of organic matter and mineral nutrients from the mid position on the slope and accumulation in the lower position. The differential sorption of herbicides by the soil samples taken at various positions along the slope was closely related to changes in organic matter content. Although sorption of bromacil and simazine varied considerably at various positions along the slope, the sorption of bromacil was very similar at depths below 30 cm regardless of positions along the slope. In the case of simazine, however, the sorption was much greater at all depths in the lower than in the upper and mid position of the slope. The sorption of both herbicides decreased considerably at depths below 30 cm at all positions along the slope, thus, indicating the potential for rapid leaching of the herbicides down the soil profile.     

Adaptation, validation and application of the chemo-thermal oxidation method to quantify black carbon in soils

The chemo-thermal oxidation method at 375 °C (CTO-375) has been widely used to quantify black carbon (BC) in sediments. In the present study, CTO-375 was tested and adapted for application to soil, accounting for some matrix specific properties like high organic carbon (≤39%) and carbonate (≤37%) content. Average recoveries of standard reference material SRM-2975 ranged from 25 to 86% for nine representative Swiss and Indian samples, which is similar to literature data for sediments. The adapted method was applied to selected samples of the Swiss soil monitoring network (NABO). BC content exhibited different patterns in three soil profiles while contribution of BC to TOC was found maximum below the topsoil at all three sites, however at different depths (60-130 cm). Six different NABO sites exhibited largely constant BC concentrations over the last 25 years, with short-term (6 months) prevailing over long-term (5 years) temporal fluctuations.     

Interception of residual nitrate from a calcareous alluvial soil profile on the North China Plain by deep-rooted crops: a 15N tracer study

15N-labeled nitrate was injected into different depths of an alluvial calcareous soil profile on the North China Plain. Subsequent movement of NO3- -N and its recovery by deep-rooted maize (Zea mays L.) and shallow-rooted eggplant (Solanum melongena L.) were studied. Under conventional water and nutrient management the mean recoveries of 15N-labeled nitrate from K(15)NO3 injected at depths 15, 45, and 75 cm were 22.4, 13.8, and 7.8% by maize and 7.9, 4.9, and 2.7% by eggplant. The recovery rate by maize at each soil depth was significantly higher than by eggplant. The deeper the injection of nitrate the smaller the distance of its downward movement and this corresponded with the movement of soil water during crop growth. Deeper rooting crops with high root length density and high water consumption may therefore be grown to utilize high concentrations of residual nitrate in the subsoil from previous intensive cropping and to protect the environment.     

Long Term Monitoring of Hydrocarbon Contamination Using Multi-Level Vapor Phase Piezometers

This study evaluated the feasibility of supplementing groundwater monitoring protocols by assessing the vadose zone for the extent of residual subsurface contamination. The study also characterized the response of the soil gas signatures with respect to different soil types and degrees of contamination. A field study was conducted at a former gasoline vending station located in Ottawa, Canada. The current state of contamination was determined by analysis of soil samples taken from boreholes. A series of 10 nested soil gas wells with monitoring depths of 0.75, 1.5, 2.25 and 3.0 m were then installed. Using these wells, soil gas surveys were performed at regular intervals over an extended period to quantify Gaseous TPH (TPH g ), oxygen and carbon dioxide concentrations in the soil gas. Results indicate that soil gas wells located near the source term exhibited characteristic soil gas signatures and significant fluctuations in TPH g , oxygen, and carbon dioxide concentrations with time. Soil gas wells located beyond the soil contamination demonstrated limited correlation between TPH g , oxygen and carbon dioxide concentrations and decreased seasonal variability.     

Phytoremediation of an arsenic-contaminated site using Pteris vittata L. and Pityrogramma calomelanos var. austroamericana: a long-term study

This field study investigated the phytoremediation potential of two arsenic (As) hyperaccumulating fern species, Pityrogramma calomelanos var. austroamericana and Pteris vittata over 27-month duration at a disused As-contaminated cattle-dip site located at Wollongbar, NSW, Australia. Ferns planted in January 2009 were harvested following 10, 22 and 27 months of growth. A detailed soil sampling was undertaken in June 2009 (initial, n?=?42 per plot) and limited sampling in April 2011 (after 27 months, n?=?15 per plot) to measure total and phosphate-extractable As concentrations in soil at 0?-?20-, 20?-?40- and 40?-?60-cm depths. The choice of the limited number of samples was considered sufficient to estimate the changes in soil As concentration following phytoremediation based on a geostatistical model. The average frond dry biomass, As concentration and As uptake were significantly (P??0.05), respectively, by P. vittata. Our results show that phytoremediation time based on observed changes in soil As based on limited sampling is not reliable; hence, it is recommended that the frond As uptake should be considered in order to evaluate the phytoremediation efficiency of the two fern species at the experimental site. Using As uptake of the two fern species, we estimate that with P. calomelanos var. austroamericana it would take 55?-?125 years to decrease mean total As content below the ecological investigation level (20 mg kg(-1)) in the surface and subsurface soils, whereas with P. vittata 143?-?412 years would be required to achieve this target.     

Transport and degradation of propyleneglycol and potassium acetate in the unsaturated zone

De-icing chemicals used during the winter season are potential pollutants for the groundwater underneath the new main airport of Norway. Several field experiments examining the transport and degradation of propyleneglycol (PG), potassium acetate (KAc) and non-reactive tracers were performed in a lysimeter trench under natural snowmelting conditions. Chemicals were applied underneath the snow cover and the transport in a heterogeneous coarse sandy soil was examined by extracting soil water from 30 or 40 suction cups placed at five depths between 0.4 and 2.4 m depth. Transport and degradation was analysed by spatial moment calculations. The de-icing chemicals showed the same basic displacement as chemically inactive tracers, an initial fast transport during the melting period followed by a period of stagnation throughout the summer season. PG seemed to be displaced to greater depths compared to non-reactive tracer after the first application. However, computer simulations of transport and degradation in a heterogeneous unsaturated soil showed that decreasing degradation constants with depth can generate a downward movement of the centre of mass without any flow occurring in the system. Potassium acetate showed some adsorption, with calculated retardation factors of approximately 1.3 and 1.2. The degradation rate constant for PG was calculated to be 0.015 day-1 in 1994 and increased to 0.047 day-1 in the second application made in 1995. The degradation rate constant for acetate was estimated to be 0.02 day-1. Increased manganese concentrations seem to be a good indicator of degradation of PG and Ac.