Extractability and Subsequent Biodegradation of PAHs from Contaminated Soil

The biodegradation of polyaromatic hydrocarbons (PAHs) has been well documented; however, the biodegradation of PAHs in contaminated soil has proved to be problematic. Sorption of PAHs to soil over time can significantly decrease their availability for extraction much less than for biodegradation. In this study the ability of various organic solvents to extract PAHs from coal tar-contaminated soil obtained from former manufactured gas plant (MGP) sites was investigated. Solvents investigated included acetone/hexane, dichloromethane, ethanol, methanol, toluene, and water. The extraction of MGP soils with solvents was investigated using soxhlet extraction, multiple soxhlet extractions, sonication, and brief agitation at ambient temperature with a range of solvent concentrations. Of particular interest was the documentation of the recalcitrance of PAHs in weathered MGP soils to extraction and to bioremediation, as well as to demonstrate the ease with which PAHs extracted from these soils can be biodegraded. The efficiency of extraction of PAHs from MGP soils was found to be more dependent upon the choice of solvent. The environmentally-benign solvent ethanol, was shown to be equal to if not better than acetone/hexane (the EPA recommended solvent) for the extraction of PAHs from MGP soils, brief contact/agitation times (minutes) using small quantities of ethanol (2 volumes or less) can achieve nearly quantitative extraction of PAHs from MGP soils. Moreover aqueous slurries of an MGP soils experienced less than 10% biodegradation of PAHs in 14 days while in the same period about 95% biodegradation was acieved using PAHs extracted from this soil by ethanol and subsequently added to aqueous bacterial suspensions.     

Effects of Soil Drying on Soil pH and Nutrient Extractability

A sample set from a field experiment conducted at two sites, a commercial organic potato farm and a conventionally managed experiment station farm, was used to compare the extractability of nutrients in field-moist and air-dried soils. Standard soil characterization methods of the Maine Soil Testing Service were used to determine soil pH and extractable nutrient content. The data were analyzed with Systat using paired t-tests. Air drying decreased soil pH and increased extractability of calcium, micronutrients, and metals. Many of the observed changes were probably a result of increasing surface acidity with drying. Drying increased the extractability of inorganic phosphorus, probably because of disruption of aluminophosphate complexes, particularly in conventionally managed soils, which had received high amounts of inorganic phosphorus fertilizer. Drying also increased the extractability of complexed phosphorus, probably both organically and inorganically complexed phosphorus, and decreased the extractability of potassium, probably by enhancing potassium fixation in clay interlayers.     

苯磺隆和2,4-D胁迫对土壤微生物影响的研究

以盆栽试验研究了除草剂苯磺隆、2,4-D对石灰性褐土中土壤微生物群落的影响。结果表明,在供试浓度下,土壤微生物对两种除草剂的感应存在一定的差异性。苯磺隆高浓度处理在最初3d极显著地抑制细菌生长,之后对土壤细菌具有刺激作用,特别是培养结束时激活率还高达917.6%,低浓度处理呈极显著的刺激作用;苯磺隆对土壤放线菌具有显著的刺激作用,对土壤真菌有强烈的抑制作用,最高抑制率达100%,到培养结束时(60d)真菌数量还未恢复到对照水平。2,4-D处理对土壤放线菌具有明显的抑制、激活的波动性,对土壤细菌、真菌有强烈的抑制作用。     

Leaching of 2,4-D and dicamba from home lawns

Leaching of the broadleaf herbicides 2,4-D and dicamba from home lawns was monitored with ceramic extraction plates placed at a 0.2 m depth beneath undisturbed sod. The site was located on a Merrimac sandy loam. Four treatments, consisting of two rates of herbicide applications coupled with two irrigation regimes. were evaluated on 12 plots. The low herbicide rate consisted of 1.1 and 0.1 kg ha^?1 yr^?1 of 2,4-D and dicamba, respectively. The high rate used was 3.3 and 0.33 kg ha^?1 yr^?1 of 2,4-D and dicamba applied in three equal applications. Irrigation treatments were (1) minimal irrigation to avoid drought stress and percolation from the root zone and (2) overwatering at 37.5 mm week^?1. Geometric mean concentra tions of 2,4-D ranged from 0.55 to 0.87 μg L^?1 compared to 0.26 to 0.55 μg L^?1 for dicamba. The low application-minimum irrigation treatment generated significantly higher concentrations than the other treatments for both herbicides. The low concentrations observed for both herbicides suggest that excellent degradation conditions exist in the root zone of turfgrass during the summer months when application occurs.     

Extractability and Bioavailability of Mercury from a Mercury Sulfide Contaminated Soil in Oak Ridge, Tennessee, USA

Historically as part of its national security mission, the U.S. Department of Energy’s Y-12 National Security Facility in Oak Ridge, TN acquired a significant fraction of the world’s supply of elemental mercury. During the 1950s and 1960s, a large amount of elemental mercury escaped confinement and is still present in the watershed surrounding the Y-12 facility. A series of remediation efforts have been deployed in the watersheds around the Oak Ridge site. However, most recently, concentration of total mercury in fish and water of the lower East Fork Poplar Creek (EFPC) of Oak Ridge has increased although majority of the mercury contamination in the local soils is present in the form of mercury sulfide. We have studied the extractability, solubility, and bioavailability of mercury sulfide in Oak Ridge soils. Dynamics of the dissolution of mercury sulfide by various extractants, including acids and a chelating agent, have been investigated. After three seasons of planting, soil mercury sulfide is more easily dissolved by both 4 M and 12 M nitric acid than is pure mercury sulfide reagent as indicated by their dissolution kinetics. Mercury release by EDTA from HgS-contaminated soil increased with time of reaction and soil mercury level. This chelating chemical increases the solubility of mercury in HgS-contaminated Oak Ridge soil. The results also show that mercury sulfide in contaminated Oak Ridge soils was still to some extent bioavailable to plants. The increase of bioavailability of soil mercury sulfide after three seasons of planting may contribute to the recent increase of mercury levels in water of the Lower East Fork Popular Creek (LEFPC) of Oak Ridge.     

Evaluation of Different Soil Tests for Phosphate Extractability in Major Soils from Angola

Phosphate (P) extractability was evaluated in twenty-eight superficial and subsuperficial horizons of representative soils occurring in Angola: Typic ferrallitic, weakly ferrallitic, Psammoferrallitic, Eutroparaferrallitic, and Fersilliatic soils. These soils show a wide range of texture, pH, cation exchange capacity, contents of organic C, and active noncrystalline forms of aluminum and iron extracted by acidified ammonium oxalate. Soil P was evaluated using eight different extractants, corresponding to the following tests: distilled water (Pdw), 0.01 M calcium chloride (CaCl₂) (Pca), iron oxide–impregnated filter paper (Pfe), Bray 2 (Pb2), Mehlich 3 (Pm3), Egnér–Riehm (Peg), Olsen (Pol), and acidified ammonium oxalate (Pox). The overall P extractability by the different tests was in the order Pca < Pdw < Peg < Pfe ≈ Pol < Pm3 < Pb2 < Pox. In the surface and subsurface horizons, the orders were Pca < Pdw < Peg < Pfe ≈ Pol < Pm3 < Pb2 < Pox and Pca < Pdw < Peg < Pfe ≈ Pm3 ≈ Pol < Pb2 < Pox, respectively. Very low amounts of P were extracted by the Pdw and Pca tests, making their use for agronomic purposes limited. The abilities of the Pfe and Pol tests to extract P in study soils were similar. The Peg test showed less ability to extract P than the Pb2 and Pm3 tests. The Pox test showed strong ability to dissolve P bound by amorphous iron and aluminum. The high positive correlation between the Pfe test and labile bioavailable P may warrant the use of Pb2, Pm3, Peg, and Pol tests to predict the amounts of labile bioavailable P for Angolan soils. Nevertheless, the little amounts of P extracted by Peg test could make it difficult to establish fertility classes. The main sources of P extracted by studied tests were mostly surfaces of active noncrystalline (amorphous or poorly crystalline inorganic) and organically complexed forms of iron and aluminum. Future work is necessary to assess the agronomic and the environmental meaning of these tests in Angolan soils.     

Fate of 14C-ring-labeled 2,4-D, 2,4-dichlorophenol and 4-chlorophenol during straw composting

Experiments were carried out to study the transformation of ¹⁴C-ring-labeled 2,4-D and the two related chlorophenols 4-chlorophenol (4-CP) and 2,4-dichlorophenol (4-DCP) during straw composting under controlled laboratory conditions. Incubation under sterile and nonsterile conditions was done to evaluate the relative importance of the biotic and abiotic processes. Pre-composted straw was treated with the three chemicals. The availability of the different chemicals was monitored during incubations as well as their degradation. Under nonsterile conditions, the mineralization of both chlorophenols reached 20% of the applied compounds, whereas it was 52% for 2,4-D. Transitory water-soluble metabolites of 2,4-D and chlorophenols were formed but they disappeared rapidly. After 21 days, 21% of the 2,4-D and 38% of the 2,4-DCP was stabilized as nonextractable (bound) residues under nonsterile conditions. Bound residues of both chemicals were negligible under sterile conditions. Availability of chemicals as estimated by water extraction decreased during incubation proportionally to mineralization and to the formation of bound residues. The increase in immobilization of the chemical residues was stronger under nonsterile conditions than under sterile conditions. Under nonsterile conditions 71% of the 4-CP was recovered as bound residues, whereas under sterile conditions 30% of the applied 4-CP formed bound residues after formaldehyde addition and only 8% with autoclaved straw. Global microbial activity decreased in the presence of the chlorophenols probably due to their toxic effect. These data indicate that the biological activity associated with straw transformation during composting stimulates the depletion of 2,4-D and chlorophenols by mineralization and by formation of bound residues. Received: 6 September 1996     

2,4-D丁酯的水解与光解特性研究

通过室内模拟试验,研究2,4-D丁酯在不同pH值和温度下的水解动态和在有机溶剂中的光解特性。结果表明,2,4-D丁酯的水解与光解均符合一级动力学方程。在pH7以下的缓冲溶液中,2,4-D丁酯的水解反应十分缓慢,但在碱性溶液中其水解速率加快。25℃下2,4-D丁酯在pH5、7和9的缓冲溶液中的水解半衰期分别为23.5、5.8d和10.7min。2,4-D丁酯的水解速率随温度升高而增加,在温度为15、25℃和35℃的pH7缓冲溶液中的水解半衰期分别为21.5、5.8、3.9d,平均温度效应系数为2.57。2,4-D丁酯水解反应的活化能与温度之间无明显相关性,而活化熵与温度呈显著相关性。2,4-D丁酯的水解主要由活化熵所驱动。采用GC-MS技术对2,4-D丁酯水解产物进行鉴定,确定水解产物主要是2,4-二氯苯氧乙酸和2,4-二氯苯酚。2,4-D丁酯在正己烷中光解速率比在甲醇中快,在丙酮中几乎不发生光解,其光解速率随浓度的升高而减慢。     

The millimetre-scale distribution of 2,4-D and its degraders drives the fate of 2,4-D at the soil core scale

The biodegradation of organic compounds in soil is a key process that has major implications for different ecosystem services such as soil fertility, air and water quality, and climate regulation. Due to the complexity of soil, the distributions of organic compounds and microorganisms are heterogeneous on sub-cm scales, and biodegradation is therefore partly controlled by the respective localizations of organic substrates and degraders. If they are not co-localized, transfer processes become crucial for the accessibility and availability of the substrate to degraders. This spatial interaction is still poorly understood, leading to poor predictions of organic compound dynamics in soils. The objectives of this work were to better understand how the mm-scale distribution of a model pesticide, 2,4-dichlorophenoxyacetic acid (2,4-D), and its degraders drives the fate of 2,4-D at the cm soil core scale. We constructed cm-scale soil cores combining sterilized and “natural” soil aggregates in which we controlled the initial distributions of 2,4-D and soil microorganisms with the following spatial distributions: i) a homogeneous distribution of microorganisms and 2,4-D at the core-scale, ii) a co-localized distribution of microorganisms and 2,4-D in a single spot (360 mm³) and iii) a disjoint localization of microorganisms and 2,4-D in 2 soil spots (360 mm³) separated by 2 cm. Two sets of experiments were performed: one used radiolabeled ¹⁴C-2,4-D to study the fate of 2,4-D, and the other used ¹²C-2,4-D to follow the dynamics of degraders. Microcosms were incubated at 20 °C and at field capacity (−31.6 kPa). At the core scale, we followed 2,4-D mineralization over time. On three dates, soil cores with microorganisms and 2,4-D localized in soil spots, were cut out in slices and then in 360 mm³ soil cubes. The individual soil cubes were then independently analysed for extractable and non-extractable ¹⁴C and for degraders (quantitative PCR of tfdA genes). Knowing the initial position of each soil cube allowed us to establish 3D maps of 2,4-D residues and degraders in soil. The results indicated that microorganisms and pesticide localizations in soil are major driving factors of i) pesticide biodegradation, by regulating the accessibility of 2,4-D to degrading microorganisms (by diffusion); and ii) the formation of non-extractable residues (NER). These results also emphasized the dominant role of microorganisms in the formation and localization of biogenic NER at a mm-scale. To conclude, these results demonstrate the importance of considering micro-scale processes to better understand the fate of pesticides and more generally of soil organic substrates at upper scales in soil and suggest that such spatial heterogeneity should not be neglected when predicting the fate of organic compounds in soils.     

田间条件下施用石灰石及调理剂降低土壤镉可提取性的效应

原位钝化是镉污染稻田土壤修复的主要方法之一,钝化剂的选择对修复效果十分关键.通过3个田间试验和示范区对比调查研究了施用石灰石及主要调理剂对稻田土壤镉的钝化效应,并提出有效的技术措施.结果表明,施用足量石灰石(≥3.75 t/hm2,试验Ⅰ)、钙镁磷肥(3.75 t/hm2,试验Ⅲ)和生物质炭(9.00 t/hm2,试验...     

Sorption of 2,4-D and other phenoxy herbicides to soil, organic matter, and minerals

Purpose

We review 2,4-dichlorophenoxyacetic acid (2,4-D) and other phenoxy herbicide sorption experiments.

Methods

A database with 469 soil–water distribution coefficients K _d (in liters per kilogram) was compiled: 271 coefficients are for the phenoxy herbicide 2,4-D, 9 for 4-(2,4-dichlorophenoxy)butyric acid, 18 for 2-(2,4-dichlorophenoxy)propanoic acid, 109 for 2-methyl-4-chlorophenoxyacetic acid, 5 for 4-(4-chloro-2-methylphenoxy)butanoic acid, and 57 for 2-(4-chloro-2-methylphenoxy)propanoic acid. The following parameters characterizing the soils, solutions, or experimental procedures used in the studies were also compiled if available: solution CaCl₂ concentration, pH, pre-equilibration time, temperature, soil organic carbon content (f _oc), percent sand, silt and clay, oxalate extractable aluminum, oxalate extractable iron (Oxalate Fe), dithionite–citrate–bicarbonate extractable aluminum, dithionite–citrate–bicarbonate extractable iron (DCB Fe), point of zero negative charge, anion exchange capacity, cation exchange capacity, soil type, soil horizon or depth of sampling, and geographic location. K _d data were also compiled characterizing phenoxy herbicide sorption to the following well-defined sorbent materials: quartz, calcite, α-alumina, kaolinite, ferrihydrite, goethite, lepidocrocite, soil humic acid, Fluka humic acid, and Pahokee peat.

Results

The data review suggests that sorption of 2,4-D can be rationalized based on the soil parameters pH, f _oc, Oxalate Fe, and DCB Fe in combination with sorption coefficients measured independently for humic acids and ferrihydrite, and goethite.

Conclusions

Soil organic matter and iron oxides appear to be the most relevant sorbents for phenoxy herbicides. Unfortunately, few authors report Oxalate Fe and DCB Fe data.     

Sorption Studies of 2,4-D on Selected Soils

Adsorption/desorption characteristics of the herbicide 2,4-D on various types of soils were investigated. Batch equilibrium techniques were used in the laboratory experiments. Data were fitted to the linear and Freundlich sorption equations. K and Kf values ranged between 0.32–1.89 L- 1 mg and 2.6 × 10-3 – 7.4 mg kg- 1, respectively. Results showed that both for linear and Freundlich adsorption equations, for all soils, K and Kf were correlated to the organic matter content (r = 0.87 and r = 0.66, respectively). Adsorption was also positively correlated with silt and clay content of soils (r = 0.53) and negatively correlated with sand content.     

Effect of Organic Materials on Partitioning,Extractability and Plant Uptake of Metals in an Alum Shale Soil

Soils developed on sulphide-bearing shale (alum shale) in Norway contain naturally high amount of heavy metals. We conducted a greenhouse pot experiment to study the effect of four rates (0, 2, 4, and 8%) and three sources (cow manure, pig manure and peat soil) of organic matter in partitioning and distribution, extractability and plant uptake of Cd, Cu, Ni and Zn in an alum shale soil. Sequential extraction scheme was used to determine the distribution patterns of metals in the soil. DTPA was used for extracting the metals from the soil. Wheat (Triticum aestivum) was used as a test crop to study the plant uptake of metals. The highest amount of Cd was present in the exchangeable fraction, irrespective of the rate and source of organic matter applied. Copper, Ni, and Zn, on the other hand, were present only in small quantities in this fraction. The largest fraction of Cu was associated with organic matter and the amounts present in the oxide, carbonate and exchangeable fractions were very small. Nickel and Zn were found mainly in the residual fraction. Increasing rates of cow and pig manure decreased the amounts of Cd and Ni associated with the exchangeable fraction whereas, the addition of peat soil at the same rate increased the amounts of these metals associated with this fraction. This effect of organic matter was primarily associated with the change in soil pH caused by different organic matter sources. The DTPA-extractable metals were decreased with increasing rates of organic matter application, irrespective of its source. Grain and straw yields of wheat were decreased with increasing rates of organic matter. The application of organic matter increased the Cu and Zn concentrations in both grain and straw. The concentration of all metals was lower in plants grown in the cow manure amended soil as compared to those grown in the soil amended with either pig manure or peat soil. These results sugggest that the source of organic matter was a determining factor for metal distribution in the soil and for metal uptake by plants. In this study cow manure slightly increased the soil pH and thus was more effective than either pig manure or peat soil in reducing the plant uptake of metals but in general the efficiency of the organic material in reducing heavy metal uptake was small.     

Dissipation of 2,4-D glyphosate and paraquat in river water

Dissipation of herbicides in river water was determined by adding different concentrations of 2,4-D, glyphosate and paraquat to samples of river water. A small variation of dissipation of radioactivity for¹⁴C-2,4-D in higher and lower concentrations and in different samples of river water was found. But about half the radioactivity disappeared from water samples of original glyphosate concentration at 100 mg L^?1 and, in the case of 100 μg L^?1, only 11 to 22% remained in the samples of river water after 56 d incubation except the sample from Hsin-Tien River. More than 80% of paraquat remained in water samples. Determination of octanol-water partition coefficient (Kow) showed a large difference in amounts of 2,4-D partitioned in water phase at different pH values, 97.4% at the higher pH of ionic state and 5.2% at the lower pH of molecular state, implying that pH value of water might affect the bioaccumulation process of 2,4-D. The result showed that 95.0% of glyphosate present in water phase in ionic form (higher pH) and 82.3% in molecular form (lower pH), indicating that glyphosate might have no affect on the biomagnification, since most of glyphosate could be excreted with water by organisms.     

Extractability and Transformation of Copper and Zinc Added to Tropical Savanna Soil under Long-Term Pasture

The extractability and slow reactions of copper (Cu) and zinc (Zn) in a weathered savanna soil under Brachiaria decumbens, Digitaria smutsii, and Stylosanthes guianensis pastures were determined in a laboratory incubation study using a sequential extraction to remove operationally defined fractions of the metals, consisting of exchangeable, organically bound, precipitate [occluded in aluminum (Al) and iron (Fe) oxides], and residual metal fractions. The soils from the pasture fields were spiked with 100 mg Cu kg^–1 soil and 200 mg Zn kg^–1 soil for 24 weeks. Copper and Zn extractable with 1 N potassium nitrate (KNO₃) solution decreased exponentially with time but reached a steady state after 2–3 weeks. The concentrations of Cu and Zn exchangeable with potassium (K) were greater in the Digitaria smutsii field soil than Brachiaria decumbens and Stylosanthes guianensis field soils. The exchangeability of added Cu and Zn (indexed Mⁿ⁺ _(exch)) with time was described by a simple exponential decay equation: Mⁿ⁺ _(exch) = αe^βt, where α is a constant, β is a coefficient that defines the rate of transformation of added Cu and Zn from the exchangeable to nonexchangeable pools, and t is time. The β values for Cu (0.040–0.076 mg kg^–1 d^–1) were almost 10 times greater than those of Zn (0.005–0.007 mg kg^–1 d^–1). Sequential extraction of added Cu and Zn indicated that between 26 and 30% of the total Cu and between 19 and 30% of the total Zn were associated with organic matter. Similarly, between 35 and 38% of total Cu and between 47 and 60% of total Zn were associated with Fe, Al, and manganese (Mn) oxides. The differential capacity of the pasture fields to transform added Cu and Zn from exchangeable and labile form to nonlabile and nonexchangeable form appears to be governed by organic matter (OM), pH, and active Fe ratio in the pasture field soils.     

Behaviour of 2,4-D Herbicide in Coastal Area of Oka River,Russia

Laboratory and field experiments werecarried out with 2,4-D herbicide(2,4-Dichlorophenoxyacetic acid) to evaluate itstransformation and migration in the coastal waterprotection zones of the Oka river, Russia. In thefirst laboratory experiment, the transformation of2,4-D was studied in various soil samples from coastalslopes (1–0°) of 480 m length soil-geochemicalcatena on the right side of the Oka river incomparison with watershed and floodplain soils. Thetransformation of 2,4-D was the lowest in soil sampleswith minimal pH values and was independent of eitherslope values or vicinity to the Oka river channel.Using indirect estimates, the surface runoff potentialwas calculated for this herbicide. In the second fieldexperiment, the vertical migration and transformationof 2,4-D was carried out in soddy sand soil (EutricArenosol) placed in the left side of the Oka river(0-100 cm) under `soft' (40 mm 2 hr<sup>-1</sup>) and `hard'(40 mm 15 min^-1) irrigation regimes. Furthermore, thetransformation of this herbicide was studied in 0–20and 40–50 cm soil layers under various temperature andmoisture regimes. After 1 day of irrigation, the mainherbicide quantity was found in the 0–30 cm layerunder both irrigation regimes. The transformation ofthe herbicide was faster in the surface, 0–20 cmlayer, than in the deeper, 40–50 cm layer.     

Accumulation of 2,4-D and glyphosate in fish and water hyacinth

At a concentration of approximately one hundredth and one thousandth of the 48-hr LC₅₀ values, the accumulation of radioactivity and relative concentration of 2,4-D and glyphosate in carp and tilapia were studied by using labelled and unlabelled chemicals. About 83 (at a concentration of 0.5 ppm) and 91% (of 0.05 ppm) of the radioactive matter remained in the water until 14 days after ¹⁴C-2,4-D amended, but only 17.2% of glyphosate remained in the water with 0.05 ppm concentration of glyphosate. No significant variation was shown in the accumulation of the concentration of herbicide in fish from 2 to 7 d. Although glyphosate disappeared within 3 d in water under sunlight, the radiochemicals in the water hyacinth remained constant to the 14th d.