Volatilization of 1,2-dibromo-3-chloropropane (DBCP) from soils.

The volatilization of DBCP from soils, as affected by the soil characteristics and application techniques, was studied in a laboratory experiment. The volatilization rate of DBCP applied in water was higher from sandy and silty loam soils than from clay soil. Water added after DBCP application acted as a soil cover, decreasing the volatilization rate. The results obtained with DBCP application in hexane to air-dry soils, indicate that adsorption could be an important factor in reducing the volatilization losses. Diffusion coefficients were calculated from the volatilization parameters, by using a simplified relationship between volatilization losses and diffusion through soil.     

Fate and transport of monoterpenes through soils. Part I. Prediction of temperature dependent soil fate model input-parameters

Monoterpenes are C10H(n)O(n') compounds of natural origin and are potentially environmentally safe substitutes for traditional pesticides. Still, an assessment of their environmental behaviour is required. As a first step in a theoretical study focussing on monoterpenes applied as pesticides to terrestrial environments, soil fate model input-parameters were determined for 20 monoterpenes with widely different structural characteristics. Input-parameters are the water solubility (S(W)), vapour pressure (P), n-octanol-water partition coefficient (K(OW)), atmospheric air and bulk water diffusion coefficients (D(A)air and D(W)water), first order biodegradation rate constants (k), and their temperature dependence. Values for these parameters were estimated or taken from previous experimental work. The quality of the estimations was discussed by focussing on their statistics and by comparison with available experimental data. From these properties, the air-water partition coefficient (K(AW), Henry's Law constant), the interface-water partition coefficient (K(IW)) and the organic matter-water partition coefficient (K(OM)) could be estimated with varying levels of accuracy. In general, little experimental data turned out to be available on biodegradation rate constants and on the temperature dependence of physico-chemical parameters.     

A column method for determination of leaching of polycyclic aromatic hydrocarbons from aged contaminated soil

In this study a column leaching method for investigation of hydrophobic organic contaminants (HOCs) leaching from soil was developed. The method set-up is based on a recycled flow of sterile water through a soil column with a sedimentation chamber mounted on top of the column, in connection with on-line filtration. The combination of a sedimentation chamber and an on-line filtration enables the measurement of leaching concentrations from contaminated materials consisting of very fine particle fractions. In addition, by using on-line solid phase extraction, minute amounts of leaching HOCs may be captured and quantified with high accuracy and reproducibility. The method was applied successfully on a contaminated aged soil sample and the leaching behavior of seven PAHs, with three to six aromatic rings, was monitored for more than 1600 h under saturated conditions. The tested PAHs were fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)pyrene and benzo(ghi)perylene. The method proved to be reliable and capable of providing data on leachable amounts of the PAHs under field-like conditions and over a longer period of time. The results indicated low availability of the studied contaminants since only a minor fraction (0.3%) of the initial amount of PAHs in the soil was removed during the experiment (liquid/solid-ratio of 700 l/kg). Thus PAHs in aged contaminated soil are not to be expected to be released to any great extent only by leaching with water.     

Volatilization of 1,2‐dibromo‐3‐chloropropane (DBCP) from soils

Abstract

The volatilization of DBCP from soils, as affected by the soil characteristics and application techniques, was studied in a laboratory experiment. The volatilization rate of DBCP applied in water was higher from sandy and silty loam soils than from clay soil. Water added after DBCP application acted as a soil cover, decreasing the volatilization rate. The results obtained with DBCP application in hexane to air‐dry soils, indicate that adsorption could be an important factor in reducing the volatilization losses.

Diffusion coefficients were calculated from the volatilization parameters, by using a simplified relationship between volatilization losses and diffusion through soil.     

影响有机污染物在土壤中的迁移、转化行为的因素

本文介绍了有机污染物在土壤中的吸附与解吸附、渗滤、挥发和降解等行为过程。探讨了吸附与解吸附机理、土壤有机质含量和类型、水分含量及温度等对此过程的影响。依据某些典型的化合物行为模型,论述了影响土壤中有机污染物渗滤的因素。有机污染物需要先从土壤深层迁移至地表,然后挥发至大气,在土壤中迁移的速率较慢,控制着整个挥发过程,可用Ｆｉｃｋ 第二定律来描述。有机污染物在土壤中的非生物降解主要包括氧化－ 还原、光解和水解等反应。土壤中的Ｏ２ 含量、土壤有机质成分和含量、辐射强度、光谱分布、土壤水分含量、温度和ｐＨ 值等都会影响非生物降解过程。其中有些因素通过影响微生物的生物活性,还影响有机污染物的生物降解     

Biostimulation and bioaugmentation enhances aerobic biodegradation of dichloroethenes

The accumulation of dichloroethenes (DCEs) as dominant products of microbial reductive dechlorination activity in soil and water represent a significant obstacle to the application of bioremediation as a remedial option for chloroethenes in many contaminated systems. In this study, the effects of biostimulation and/or bioaugmentation on the biodegradation of cis- and trans-DCE in soil and water samples collected from contaminated sites in South Africa were evaluated in order to determine the possible bioremediation option for these compounds in the contaminated sites. Results from this study indicate that cis- and trans-DCE were readily degraded to varying degrees by natural microbial populations in all the soil and water samples tested, with up to 44% of cis-DCE and 41% of trans-DCE degraded in the untreated soil and water samples in two weeks. The degradation rate constants ranged significantly (P<0.05) between 0.0938 and 0.560 wk(-1) and 0.182 and 0.401 wk(-1), for cis- and trans-DCE, respectively, for the various treatments employed. A combination of biostimulation and bioaugmentation significantly increased the biodegradation of both compounds within two weeks; 14% for cis-DCE and 18% for trans-DCE degradation, above those observed in untreated soil and water samples. These findings support the use of a combination of biostimulation and bioaugmentation for the efficient biodegradation of these compounds in contaminated soil and water. In addition, the results clearly demonstrate that while naturally occurring microorganisms are capable of aerobic biodegradation of cis- and trans-DCE, biotransformation may be affected by several factors, including isomer structure, soil type, and the amount of nutrients available in the water and soil.     

Stabilization of Pb- and Cu-contaminated soil using coal fly ash and peat

The stabilization of metal contaminated soil is being tested as an alternative remediation method to landfilling. An evaluation of the changes in Cu and Pb mobility and bioavailability in soil induced by the addition of coal fly ash and natural organic matter (peat) revealed that the amount of leached Cu decreased by 98.2% and Pb by 99.9%, as assessed by a batch test. Metal leaching from the treated soil was lower by two orders of magnitude compared to the untreated soil in the field lysimeters. A possible formation of mineral Cu- and Pb-bearing phases and active surface with oxides were identified by chemical equilibrium calculations. Low metal leaching during a two-year observation period, increased seed germination rate, reduced metal accumulation in plant shoots, and decreased toxicity to plants and bacteria, thereby demonstrating this stabilization method to be a promising technique for in situ remediation of Cu and Pb contaminated soil.     

A reactive transport model for mercury fate in soil—application to different anthropogenic pollution sources

Soil systems are a common receptor of anthropogenic mercury (Hg) contamination. Soils play an important role in the containment or dispersion of pollution to surface water, groundwater or the atmosphere. A one-dimensional model for simulating Hg fate and transport for variably saturated and transient flow conditions is presented. The model is developed using the HP1 code, which couples HYDRUS-1D for the water flow and solute transport to PHREEQC for geochemical reactions. The main processes included are Hg aqueous speciation and complexation, sorption to soil organic matter, dissolution of cinnabar and liquid Hg, and Hg reduction and volatilization. Processes such as atmospheric wet and dry deposition, vegetation litter fall and uptake are neglected because they are less relevant in the case of high Hg concentrations resulting from anthropogenic activities. A test case is presented, assuming a hypothetical sandy soil profile and a simulation time frame of 50 years of daily atmospheric inputs. Mercury fate and transport are simulated for three different sources of Hg (cinnabar, residual liquid mercury or aqueous mercuric chloride), as well as for combinations of these sources. Results are presented and discussed with focus on Hg volatilization to the atmosphere, Hg leaching at the bottom of the soil profile and the remaining Hg in or below the initially contaminated soil layer. In the test case, Hg volatilization was negligible because the reduction of Hg²⁺ to Hg⁰ was inhibited by the low concentration of dissolved Hg. Hg leaching was mainly caused by complexation of Hg²⁺ with thiol groups of dissolved organic matter, because in the geochemical model used, this reaction only had a higher equilibrium constant than the sorption reactions. Immobilization of Hg in the initially polluted horizon was enhanced by Hg²⁺ sorption onto humic and fulvic acids (which are more abundant than thiols). Potential benefits of the model for risk management and remediation of contaminated sites are discussed.     

Behavior of 1,3-dichloropropene and methyl isothiocyanate in undisturbed soil columns

To develop alternatives to methyl bromide (MeBr) for soil disinfection under environmental Moroccan conditions, distribution and persistence of 1,3-dichloropropene (1,3-D) and methyl isothiocyanate (MITC) were tested in undisturbed soil columns (12 cm internal diameter, 1 m length). 1,3-D was injected at a 15 cm depth and directly followed by metam-sodium (a precursor of MITC), which was applied at the soil surface of the same column using a peristaltic pump. Concerning the distribution of these fumigants in the soil profiles, our results showed that 24 h after treatment, 1,3-D and MITC were concentrated at the 0-40 cm soil layers, and reached the deeper layers 48 h later. MITC and 1,3-D dissipation was studied and the half-life (DT50) measured were 6.5 and 8 days, respectively. Total volatilization losses reached 9% for MITC and 28% for 1,3-D. MITC and 1,3-D volatilization was found to be influence by soil water contents.The results show that by reducing volatilization, photodegradation and leaching of these fumigants a suitable alternative to MeBr use is offered.     

Temporal changes in kerosene content and composition in field soil as a result of leaching

A field experiment was designed to determine the combined effect of leaching and natural attenuation on the redistribution dynamics of kerosene--a volatile petroleum hydrocarbon mixture (VPHM)--and of its selected individual components in the soil subsurface. Variables included the composition of contaminant spilled, the soil water content before contamination and the leaching pattern. Temporal changes in the residual kerosene concentration and composition in the soil subsurface of the experimental field during 39 days and leaching by 500 mm of irrigation water were determined to a depth of 100 cm. The main processes controlling contaminant attenuation were volatilization and redistribution with depth. Soil hydration status was found to affect the attenuation, redistribution and composition of VPHM in the porous media. An initial relative increase of n-alkanes in the subsurface compared with the total VPHM in the first leaching period was a result of the volatilization of low vapor pressure compounds. The redistribution of individual components in the soil profile during leaching was in accordance with their physico-chemical properties.     

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.     

The input-output balance of cadmium in a paddy field of Tokyo

Field monitoring was practiced from 2001 to 2003 to evaluate the input (irrigation, atmospheric deposition, and fertilizer application) and the output (uptake and accumulation into the above-ground biomass of rice plants and leaching) of cadmium (Cd) in a contaminated paddy field in Tokyo. The cadmium concentrations of irrigated water, open-bulk precipitation, soil solution (leaching water), rice plants collected at the harvesting stage and the chemical fertilizer and the cow manure compost applied were determined. The Cd flux of each factor was calculated by multiplying the Cd concentration by the volume or mass of the media. The annual input-output balance of Cd in the paddy field in 2001 and 2002 was estimated to be -5.44 [corrected] g ha(-1) and -2.01 [corrected] g ha(-1), respectively, indicating the loss of Cd from the paddy field, although the losses accounted for only 0.24% [corrected] and 0.089% [corrected] of the total amount of Cd in the ploughed layer soil in 2001 and 2002, respectively. Among the factors involved, the input from fertilizers (including manure compost) and the output due to the uptake by rice plants played a major role in the balance. The former largely depended on the types and amounts of fertilizers applied, and the latter on the water management practices in the paddy field, such as flooding and drainage of the surface water.     

Impact of the earthworm Lumbricus terrestris (L.) on As, Cu, Pb and Zn mobility and speciation in contaminated soils

To assess the risks that contaminated soils pose to the environment properly a greater understanding of how soil biota influence the mobility of metal(loid)s in soils is required. Lumbricus terrestris L. were incubated in three soils contaminated with As, Cu, Pb and Zn. The concentration and speciation of metal(loid)s in pore waters and the mobility and partitioning in casts were compared with earthworm-free soil. Generally the concentrations of water extractable metal(loid)s in earthworm casts were greater than in earthworm-free soil. The impact of the earthworms on concentration and speciation in pore waters was soil and metal specific and could be explained either by earthworm induced changes in soil pH or soluble organic carbon. The mobilisation of metal(loid)s in the environment by earthworm activity may allow for leaching or uptake into biota.     

Mobility of Pb, Cu, and Zn in the phosphorus-amended contaminated soils under simulated landfill and rainfall conditions

Phosphorus-bearing materials have been widely applied in immobilization of heavy metals in contaminated soils. However, the study on the stability of the initially P-induced immobilized metals in the contaminated soils is far limited. This work was conducted to evaluate the mobility of Pb, Cu, and Zn in two contrasting contaminated soils amended with phosphate rock tailing (PR) and triple superphosphate fertilizer (TSP), and their combination (P?+?T) under simulated landfill and rainfall conditions. The main objective was to determine the stability of heavy metals in the P-treated contaminated soils in response to the changing environment conditions. The soils were amended with the P-bearing materials at a 2:1 molar ratio of P to metals. After equilibrated for 2 weeks, the soils were evaluated with the leaching procedures. The batch-based toxicity characteristic leaching procedure (TCLP) was conducted to determine the leachability of heavy metals from both untreated and P-treated soils under simulated landfill condition. The column-based synthetic precipitation leaching procedure (SPLP) were undertaken to measure the downward migration of metals from untreated and P-treated soils under simulated rainfall condition. Leachability of Pb, Cu, and Zn in the TCLP extract followed the order of Zn?>?Cu?>?Pb in both soils, with the organic-C- and clay-poor soil showing higher metal leachability than the organic-C- and clay-rich soil. All three P treatments reduced leachability of Pb, Cu, and Zn by up to 89.2, 24.4, and 34.3 %, respectively, compared to the untreated soil, and TSP revealed more effectiveness followed by P?+?T and then PR. The column experiments showed that Zn had the highest downward migration upon 10 pore volumes of SPLP leaching, followed by Pb and then Cu in both soils. However, migration of Pb and Zn to subsoil and leachate were inhibited in the P-treated soil, while Cu in the leachate was enhanced by P treatment in the organic-C-rich soil. More than 73 % P in the amendments remained in the upper 0–10 cm soil layers. However, leaching of P from soluble TSP was significant with 24.3 % of P migrated in the leachate in the organic-C-poor soil. The mobility of heavy metals in the P-treated soil varies with nature of P sources, heavy metals, and soils. Caution should be taken on the multi-metal stabilization since the P amendment may immobilize some metals while promoting others’ mobility. Also, attention should be paid to the high leaching of P from soluble P amendments since it may pose the risk of excessive P-induced eutrophication.     

Arsenic mobility in contaminated lake sediments

An arsenic contaminated lake sediment near a landfill in Maine was used to characterize the geochemistry of arsenic and assess the influence of environmental conditions on its mobility. A kinetic model was developed to simulate the leaching ability of arsenic in lake sediments under different environmental conditions. The HM1D chemical transport model was used to model the column experiments and determine the rates of arsenic mobility from the sediment. Laboratory studies provided the information to construct a conceptual model to demonstrate the mobility of arsenic in the lake sediment. The leaching ability of arsenic in lake sediments greatly depends on the flow conditions of ground water and the geochemistry of the sediments. Large amounts of arsenic were tightly bound to the sediments. The amount of arsenic leaching out of the sediment to the water column was substantially decreased due to iron/arsenic co-precipitation at the water-sediment interface. Overall, it was found that arsenic greatly accumulated at the ground water/lake interface and it formed insoluble precipitates.     

Leaching of terbumeton and terbumeton-desethyl from mini-columns packed with soil aggregates in laboratory conditions

Leaching of terbumeton (TER) and terbumeton-desethyl (TED) from mini-columns packed with natural soil aggregates was investigated. Five soil samples from the Champagne area (France) with different physicochemical parameters were used. The soil samples were hand-packed into a 50 mm column in laboratory conditions. An aqueous solution of TER or TED was percolated through the column and collected effluents were analyzed for TER or TED using HPLC-DAD. The leaching experiments showed that TER and TED were moderately mobile. TED was more mobile than TER, possibly because of its higher polarity. The proportion of organic matter affected the mobility of TER and TED through soil columns (r=0.971) and leaching was lowest for soil having the highest organic matter content (5.9%). TER and TED were not significantly influenced by leaching solution composition (deionized water or CaCl(2) solution), but were strongly affected by soil packing. Packing resulted in less rapid release of compounds suggesting that unpacking may have contributed to preferential pathways through the soil columns. Increasing contact time between TER and soils before leaching decreased the mobility of TER and increased its persistence in soils. Indeed, 76% of TER was released when leaching started after a 15 h contact time whereas it was down to 26% after an aging treatment of 360 h. A proportion of TER (from 8% to 32%) and TED (from 8% to 17%) remained in soil. Associated to its high stability in soils this could in part account for a very slow transfer over the years towards the groundwater.     

The immobilisation and retention of soluble arsenic, cadmium and zinc by biochar

Water-soluble inorganic pollutants may constitute an environmental toxicity problem if their movement through soils and potential transfer to plants or groundwater is not arrested. The capability of biochar to immobilise and retain arsenic (As), cadmium (Cd) and zinc (Zn) from a multi-element contaminated sediment-derived soil was explored by a column leaching experiment and scanning electron microanalysis (SEM/EDX). Sorption of Cd and Zn to biochar’s surfaces assisted a 300 and 45-fold reduction in their leachate concentrations, respectively. Retention of both metals was not affected by considerable leaching of water-soluble carbon from biochar, and could not be reversed following subsequent leaching of the sorbant biochar with water at pH 5.5. Weakly water-soluble As was also retained on biochar’s surface but leachate concentrations did not duly decline. It is concluded that biochar can rapidly reduce the mobility of selected contaminants in this polluted soil system, with especially encouraging results for Cd.     

Behaviour of DDT under laboratory and outdoor conditions in Germany

Abstract

Experiments were conducted on adsorption, volatilization and UV‐degradation of p,p'‐DDT on soil surface, and leaching and degradation in sand columns. p,p'‐DDT was shown to adsorb stronger to soils with higher organic content. UV irradiation at 290 nm for 10 hours mineralized less than 0.1% of DDT in soil.

Results show that only 0.1% of DDT volatilized in a sun‐exposed semi‐closed quartz system. Polar compounds accounted from 1.4% after 55 days. The rate of volatilization and degradation in an open system was much higher; only 15% DDT and 7% DDE were recovered after 6 weeks in the organic extract. p,p'‐DDT was adsorbed to a great extent on the top layers of sand columns; 86% in the top 8 cm.     

Modeling transport and fate of nitrogen from urea applied to a near-trench paddy field

A simple but comprehensive model is developed to quantify N losses from urea applied to a near-trench paddy field, considering all the N-transformations such as urea hydrolysis, volatilization, nitrification, denitrification, and all the important transportations like runoff, lateral seepage, vertical leaching and crop uptake. Seasonal average data of field observations for three crop seasons were used for model calibration and validation, which showed that ammonia volatilization accounted for 26.5-29.4% of the applied N and N uptake by crop occupied 38.2-44.8%, while N losses via surface runoff, vertical leaching and lateral seepage varied from 5.6-7.7%, 4.0-4.9% to 5.0-5.3% of the applied N, respectively. These observed results were well predicted by our model, indicating that the model performed effectively at quantifying N losses via individual processes in a wide range of urea application rates and benefit for developing water and fertilizer management strategies for near-trench paddy fields.     

Movement of metolachlor and terbuthylazine in core and packed soil columns

Movement of metolachlor and terbuthylazine including a bromide tracer was studied in core and packed soil columns in PVC pipes (80 mm diameter, 15 mm depth) with two German soil types viz: silt loam and loamy silt. The breakthrough curves (BTCs) for bromide indicated some preferential flow of water both under conventional tillage (CN) and no-till (NT) simulation with silt loam soil. The herbicides leached to a greater extent in NT columns than in CN columns. Leaching was higher in loamy silt soil than in silt loam soil under CN conditions. This result is in agreement with the higher sorption capacity of silt loam having higher organic carbon compared to loamy silt having low organic carbon. Adsorption strength of the herbicides did not affect their breakthrough time, but was reflected in the slope and maximum height of the BTCs. The BTCs showed the expected inverse relationship between leaching and adsorption with greater mobility of the weakly-sorbed metolachlor than the more strongly sorbed terbuthylazine. Maximum amounts of the applied herbicides were recovered from the top soil layer in intact columns. Metolachlor was more mobile in packed columns than in core columns.