Impact of lime-stabilized biosolid application on Cu,Ni, Pb and Zn mobility in an acidic soil

A soil column leaching study was conducted on an acidic soil in order to assess the impact of lime-stabilized biosolid on the mobility of metallic pollutants (Cu, Ni, Pb and Zn). Column leaching experiments were conducted by injecting successively CaCl₂, oxalic acid and ethylenediaminetetraacetic acid (EDTA) solutions through soil and biosolid-amended soil columns. The comparison of leaching curves showed that the transport of metals is mainly related to the dissolved organic carbon, pH and the nature of extractants. Metal mobility in the soil and biosolid-amended soils is higher with EDTA than with CaCl₂ and oxalic acid extractions, indicating that metals are strongly bound to solid-phase components. The single application of lime-stabilized biosolid at a rate ranging from 15 to 30 t/ha tends to decrease the mobility of metals, while repeated applications (2?×?15 t/ha) increase metal leaching from soil. This result highlights the importance of monitoring the movement and concentrations of metals, especially in acid and sandy soils with shallow and smaller water bodies.     

Aminocyclopyrachlor sorption-desorption and leaching from three Brazilian soils

This study aimed to evaluate the sorption-desorption and leaching of aminocyclopyrachlor from three Brazilian soils. The sorption-desorption of ¹⁴C-aminocyclopyrachlor was evaluated using the batch method and leaching was assessed in glass columns. The Freundlich model showed an adequate fit for the sorption-desorption of aminocyclopyrachlor. The Freundlich sorption coefficient [K_{f (sorption)}] ranged from 0.37 to 1.34 µmol ^(1–1/n) L^1/n kg^?1 and showed a significant positive correlation with the clay content of the soil, while the K_{f (desorption)} ranged from 3.62 to 5.36 µmol ^(1–1/n) L^1/n kg^?1. The K_{f (desorption)} values were higher than their respective K_{f (sorption)}, indicating that aminocyclopyrachlor sorption is reversible, and the fate of this herbicide in the environment can be affected by leaching. Aminocyclopyrachlor was detected at all depths (0?30 cm) in all the studied soils, where leaching was influenced by soil texture. The total herbicide leaching from the sandy clay and clay soils was <0.06%, whereas, ～3% leached from the loamy sand soil. The results suggest that aminocyclopyrachlor has a high potential of leaching, based on its low sorption and high desorption capacities. Therefore, this herbicide can easily contaminate underground water resources.     

Impacts of simulated acid rain on recalcitrance of two different soils

Laboratory experiments were conducted to estimate the impacts of simulated acid rain (SAR) on recalcitrance in a Plinthudult and a Paleudalfs soil in south China, which were a variable and a permanent charge soil, respectively. Simulated acid rains were prepared at pH 2.0, 3.5, 5.0, and 6.0, by additions of different volumes of H₂SO₄ plus HNO₃ at a ratio of 6 to 1. The leaching period was designed to represent 5 years of local annual rainfall (1,200 mm) with a 33 % surface runoff loss. Both soils underwent both acidification stages of (1) cation exchange and (2) mineral weathering at SAR pH?2.0, whereas only cation exchange occurred above SAR pH?3.5, i.e., weathering did not commence. The cation exchange stage was more easily changed into that of mineral weathering in the Plinthudult than in the Paleudalfs soil, and there were some K⁺ and Mg²⁺ ions released on the stages of mineral weathering in the Paleudalfs soil. During the leaching, the release of exchangeable base cations followed the order Ca²⁺?>?K⁺?>?Mg²⁺?>?Na⁺ for the Plinthudult and Ca²⁺?>?Mg²⁺?>?Na⁺?>?K⁺ for the Paleudalfs soil. The SARs above pH?3.5 did not decrease soil pH or pH buffering capacity, while the SAR at pH?2.0 decreased soil pH and the buffering capacity significantly. We conclude that acid rain, which always has a pH from 3.5 to 5.6, only makes a small contribution to the acidification of agricultural soils of south China in the short term of 5 years. Also, Paleudalfs soils are more resistant to acid rain than Plinthudult soils. The different abilities to prevent leaching by acid rain depend upon the parent materials, types of clay minerals, and soil development degrees.     

Rapid metal extractability tests from polluted mining soils by ultrasound probe sonication and microwave-assisted extraction systems

Ultrasonic probe sonication (UPS) and microwave-assisted extraction (MAE) were used for rapid single extraction of Cd, Cr, Cu, Ni, Pb, and Zn from soils polluted by former mining activities (Mónica Mine, Bustarviejo, NW Madrid, Spain), using 0.01 mol L^?1 calcium chloride (CaCl₂), 0.43 mol L^?1 acetic acid (CH₃COOH), and 0.05 mol L^?1 ethylenediaminetetraacetic acid (EDTA) at pH 7 as extracting agents. The optimum extraction conditions by UPS consisted of an extraction time of 2 min for both CaCl₂ and EDTA extractions and 15 min for CH₃COOH extraction, at 30% ultrasound (US) amplitude, whereas in the case of MAE, they consisted of 5 min at 50 °C for both CaCl₂ and EDTA extractions and 15 min at 120 °C for CH₃COOH extraction. Extractable concentrations were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). The proposed methods were compared with a reduced version of the corresponding single extraction procedures proposed by the Standards, Measurements and Testing Programme (SM&T). The results obtained showed a great variability on extraction percentages, depending on the metal, the total concentration level and the soil sample, reaching high values in some areas. However, the correlation analysis showed that total concentration is the most relevant factor for element extractability in these soil samples. From the results obtained, the application of the accelerated extraction procedures, such as MAE and UPS, could be considered a useful approach to evaluate rapidly the extractability of the metals studied.     

The combined effects of urea application and simulated acid rain on soil acidification and microbial community structure

Our aim was to test the effects of simulated acid rain (SAR) at different pHs, when applied to fertilized and unfertilized soils, on the leaching of soil cations (K, Ca, Mg, Na) and Al. Their effects on soil pH, exchangeable H⁺ and Al³⁺ and microbial community structure were also determined. A Paleudalfs soil was incubated for 30 days, with and without an initial application of urea (200 mg N kg^?1soil) as nitrogen (N) fertilizer. The soil was held in columns and leached with SAR at three pH levels. Six treatments were tested: SAR of pH 2.5, 4.0 and 5.6 leaching on unfertilized soil (T1, T2 and T3), and on soils fertilized with urea (T4, T5 and T6). Increasing acid inputs proportionally increased cation leaching in both unfertilized and fertilized soils. Urea application increased the initial Ca and Mg leaching, but had no effect on the total concentrations of Ca, Mg and K leached. There was no significant difference for the amount of Na leached between the different treatments. The SAR pH and urea application had significant effects on soil pH, exchangeable H⁺ and Al³⁺. Urea application, SAR treated with various pH, and the interactions between them all had significant impacts on total phospholipid fatty acids (PLFAs). The highest concentration of total PLFAs occurred in fertilized soils with SAR pH5.6 and the lowest in soils leached with the lowest SAR pH. Soils pretreated with urea then leached with SARs of pH 4.0 and 5.6 had larger total PLFA concentrations than soil without urea. Bacterial, fungal, actinomycete, Gram-negative and Gram-positive bacterial PLFAs had generally similar trends to total PLFAs.     

Arsenic in marine sediments from French Mediterranean ports: Geochemical partitioning,bioavailability and ecotoxicology

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 L kg^?1) than in EST (55 L kg^?1), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.     

Effects of hydromorphology and riparian vegetation on the sediment quality of agricultural low-order streams: consequences for stream restoration

Intensive agricultural land use imposes multiple pressures on streams. More specifically, the loading of streams with nutrient-enriched soil from surrounding crop fields may deteriorate the sediment quality. The current study aimed to find out whether stream restoration may be an effective tool to improve the sediment quality of agricultural headwater streams. We compared nine stream reaches representing different morphological types (forested meandering reaches vs. deforested channelized reaches) regarding sediment structure, sedimentary nutrient and organic matter concentrations, and benthic microbial respiration. Main differences among reach types were found in grain sizes. Meandering reaches featured larger mean grain sizes (50–70 μm) and a thicker oxygenated surface layer (8 cm) than channelized reaches (40 μm, 5 cm). Total phosphorous amounted for up to 1,500 μg?g^?1 DW at retentive channelized reaches and 850–1,050 μg?g^?1 DW at the others. While N-NH₄ accumulated in the sediments (60–180 μg?g^?1 DW), N-NO₃ concentrations were generally low (2–5 μg?g^?1 DW). Benthic respiration was high at all sites (10–20 g O₂ m^?2?day^?1). Our study shows that both hydromorphology and bank vegetation may influence the sediment quality of agricultural streams, though effects are often small and spatially restricted. To increase the efficiency of stream restoration in agricultural landscapes, nutrient and sediment delivery to stream channels need to be minimized by mitigating soil erosion in the catchment.     

A laboratory-incubated redox oscillation experiment to investigate Hg fluxes from highly contaminated coastal marine sediments (Gulf of Trieste,Northern Adriatic Sea)

Mercury (Hg) mobility at the sediment–water interface was investigated during a laboratory incubation experiment conducted with highly contaminated sediments (13 μg g^-1) of the Gulf of Trieste. Undisturbed sediment was collected in front of the Isonzo River mouth, which inflows Hg-rich suspended material originating from the Idrija (NW Slovenia) mining district. Since hypoxic and anoxic conditions at the bottom are frequently observed and can influence the Hg biogeochemical behavior, a redox oscillation was simulated in the laboratory, at in situ temperature, using a dark flux chamber. Temporal variations of several parameters were monitored simultaneously: dissolved Hg (DHg) and methylmercury (MeHg), O₂, NH₄ ⁺, NO₃ ^- + NO₂ ^-, PO₄ ^3-, H₂S, dissolved Mn²⁺, dissolved inorganic and organic carbon (DIC and DOC). Under anoxic conditions, both Hg (665 ng m² day^-1) and MeHg (550 ng m² day^-1) fluxed from sediments into the water column, whereas re-oxygenation caused concentrations of MeHg and Hg to rapidly drop, probably due to re-adsorption onto Fe/Mn-oxyhydroxides and enhanced demethylation processes. Hence, during anoxic events, sediments of the Gulf of Trieste may be considered as an important source of DHg species for the water column. On the contrary, re-oxygenation of the bottom compartment mitigates Hg and MeHg release from the sediment, thus acting as a natural “defence” from possible interaction between the metal and the aquatic organisms.     

Mathematical prediction of imidacloprid persistence in two Croatian soils with different texture,organic matter content and acidity under laboratory conditions

In the present laboratory study, persistence of imidacloprid (IMI) as a function of initial insecticide concentration and soil properties in two Croatian soils (Krk sandy clay and Istria clay soils) was studied and described mathematically. Upon fitting the obtained experimental data for the higher concentration level (5 mg/kg) to mathematical models, statistical parameters (R ², scaled root mean squared error and χ ² error) indicated that the single first-order kinetics model provided the best prediction of IMI degradation in the Krk sandy clay soil, while in the Istria clay soil biphasic degradation was observed. At the lower concentration level (0.5 mg/kg), the biphasic models Gustafson and Holden models as well as the first-order double exponential model fitted the best experimental data in both soils. The disappearance time (DT₅₀) values estimated by the single first-order double exponential model (from 50 to 132 days) proved that IMI can be categorized as a moderately persistent pesticide. In the Krk sandy clay soil, resulting DT₅₀ values tended to increase with an increase of initial IMI concentration, while in the Istria clay soil, IMI persistence did not depend on the concentration. Organic matter of both experimental soils provided an accelerating effect on the degradation rate. The logistic model demonstrated that the effect of microbial activity was not the most important parameter for the biodegradation of IMI in the Istria clay soil, where IMI degradation could be dominated by chemical processes, such as chemical hydrolysis. The results pointed that mathematical modeling could be considered as the most convenient tool for predicting IMI persistence and contributes to the establishment of adequate monitoring of IMI residues in contaminated soil. Furthermore, IMI usage should be strictly controlled, especially in soils with low organic matter content where the risk of soil and groundwater contamination is much higher due to its longer persistence and consequent leaching and/or moving from soil surface prior to its degradation.     

Comparative sorption,desorption and leaching potential of aminocyclopyrachlor and picloram

Sorption and desorption of aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylic acid) were compared to that of the structurally similar herbicide picloram (4-amino-3,5,6-trichloro-2-pyridinecarboxylic acid) in three soils of differing origin and composition to determine if picloram data is representative of aminocyclopyrachlor behavior in soil. Aminocyclopyrachlor and picloram batch sorption data fit the Freundlich equation and was independent of concentration for aminocyclopyrachlor (1/n = 1), but not for picloram (1/n = 0.80–0.90). Freundlich sorption coefficients (K _f) for aminocyclopyrachlor were lowest in the eroded and depositional Minnesota soils (0.04 and 0.12 μmol ^(1–1/n) L^1/n kg^?1) and the highest in Molokai soil (0.31 μmol ^(1–1/n) L^1/n kg^?1). For picloram, K _f was lower in the eroded (0.28 μmol ^(1–1/n) L^1/n kg^?1) as compared to the depositional Minnesota soil (0.75 μmol ^(1–1/n) L^1/n kg^?1). Comparing soil to soil, K _f for picloram was consistently higher than those found for aminocyclopyrachlor. Desorption of aminocyclopyrachlor and picloram was hysteretic on all three soils. With regard to the theoretical leaching potential based on groundwater ubiquity score (GUS), leaching potential of both herbicides was considered to be similar. Aminocyclopyrachlor would be ranked as leacher in all three soils if t_1/2 was > 12.7 days. To be ranked as non-leacher in all three soils, aminocyclopyrachlor t_1/2 would have to be <3.3 days. Calculated half-life that would rank picloram as leacher was calculated to be ～15.6 d. Using the current information for aminocycloprachlor, or using picloram data as representative of aminocycloprachlor behavior, scientists can now more accurately predict the potential for offsite transport of aminocycloprachlor.     

Use of amendments to reduce leaching loss of phosphorus and other nutrients from a sandy soil in Florida

Goal, Scope and Background Transport of P from agricultural land contributes to the eutrophication of surface waters. Soil amendment is considered one of the best management practices (BMPs) to reduce P loss from sandy soils. Laboratory column leaching experiments were conducted to evaluate the effectiveness of different soil amendments in reducing P leaching from a typical sandy soil in Florida. Methods The tested amendments were CaCl₂, CaCO₃, Al(OH)₃, cellulose, and mill mud, and applied at the rate of 15 g/kg for a single amendment and each 7.5 g/kg if two amendments were combined. Leaching was conducted every four days for 32 days, 250 mL of deionized water being leached for each column per leaching event. Leachates were collected from each leaching event and analyzed for reactive P, PO₄-P, and macro and micro-elements. Results and Discussion Except for the soils amended with CaCl₂, or CaCl₂+CaCO₃, reactive P and PO₄-P leaching losses mainly occurred in the first three leaching events. Phosphorus leaching from the soils amended with CaCl₂ or CaCl₂+CaCO₃ was less but more persistent than that of other amendments. Reactive Pleaching loss was reduced by 36.0% and 40.4% for the amendments of CaCl₂, and CaCl₂+CaCO₃, respectively, as compared with chemical fertilizer alone, and the corresponding values for PO₄-P were 70.8% and 71.9%. The concentrations of K, Mg, Cu, and Fe in leachate were also decreased by CaCl₂ or CaCl₂+CaCO₃ amendment. Among the seven amendments, CaCl₂, CaCO₃, or their combination were most effective in reducing P leaching from the sandy soil, followed by cellulose and Al(OH)₃, the effects of mill mud and mill mud + Al(OH)₃ were marginal. Conclusions These results indicate that the use of CaCl₂, CaCO₃, or their combination can significantly reduce P leaching from sandy soil, and should be considered in the development of BMPs for the sandy soil regions. Recommendations and Outlook Most agricultural soils in south Florida are very sandy with minimal holding capacities for moisture and nutrients. Repeated application of fertilizer is necessary to sustain desired yield of crops on these soils. However, eutrophication of fresh water systems in this area has been increasingly concerned by the public. Losses of P from agricultural fields by means of leaching and surface runoff are suspected as one of the important non-point contamination sources. The benefits and effectiveness of soil amendment in reducing P losses from cropping production systems while sustaining desired crop yield need to be demonstrated. Calcium chloride, CaCO₃, or their combination significantly reduce Pleaching from sandy soil, and should be considered in the development of BMPs for the sandy soil regions.     

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.     

Sorption of selected pesticides on soils,sediment and straw from a constructed agricultural drainage ditch or pond

Buffer zones such as ponds and ditches are used to reduce field-scale losses of pesticides from subsurface drainage waters to surface waters. The objective of this study was to assess the efficiency of these buffer zones, in particular constructed wetlands, focusing specifically on sorption processes. We modelled the sorption processes of three herbicides [2-methyl-4-chlorophenoxyacetic acid (2,4-MCPA), isoproturon and napropamide] and three fungicides (boscalid, prochloraz and tebuconazole) on four substrates (two soils, sediment and straw) commonly found in a pond and ditch in Lorraine (France). A wide range of Freundlich coefficient (K _fads) values was obtained, from 0.74 to 442.63 mg^1???n ?L ⁿ ?kg^?1, and the corresponding K _foc values ranged from 56 to 3,725 mg^1???n ?L ⁿ ?kg^?1. Based on potential retention, the substrates may be classified as straw >> sediments > soils. These results show the importance of organic carbon content and nature in the process of sorption. Similarly, the studied pesticides could be classified according to their adsorption capacity as follows: prochloraz >> tebuconazole–boscalid > napropamide >> MCPA–isoproturon. This classification is strongly influenced by the physico-chemical properties of pesticides, especially solubility and K _oc. Straw exhibited the largest quantity of non-desorbable pesticide residues, from 12.1 to 224.2 mg/L for all pesticides. The presence of plants could increase soil–sediment sorption capacity. Thus, establishment and maintenance of plants and straw filters should be promoted to optimise sorption processes and the efficiency of ponds and ditches in reducing surface water pollution.     

Effect of soil and sediment composition on acetochlor sorption and desorption

Background, aim, and scope  Herbicide fate and its transport in soils and sediments greatly depend upon sorption–desorption processes. Quantitative determination of herbicide sorption–desorption is therefore essential for both the understanding of transport and the sorption equilibrium in the soil/sediment–water system; and it is also an important parameter for predicting herbicide fate using mathematical simulation models. The total soil/sediment organic carbon content and its qualitative characteristics are the most important factors affecting sorption–desorption of herbicides in soil or sediment. Since the acetochlor is one of the most frequently used herbicides in Slovakia to control annual grasses and certain annual broad-leaved weeds in maize and potatoes, and posses various negative health effects on human beings, our aim in this study was to investigate acetochlor sorption and desorption in various soil/sediment samples from Slovakia. The main soil/sediment characteristics governing acetochlor sorption–desorption were also identified. Materials and methods  The sorption–desorption of acetochlor, using the batch equilibration method, was studied on eight surface soils, one subsurface soil and five sediments collected from the Laborec River and three water reservoirs. Soils and sediments were characterized by commonly used methods for their total organic carbon content, distribution of humus components, pH, grain-size distribution, and smectite content, and for calcium carbonate content. The effect of soil/sediment characteristics on acetochlor sorption–desorption was examined by simple correlation analysis. Results  Sorption of acetochlor was expressed as the distribution coefficient (K _d). K _d values slightly decreased as the initial acetochlor concentration increased. These values indicated that acetochlor was moderately sorbed by soils and sediments. Highly significant correlations between the K _d values and the organic carbon content were observed at both initial concentrations. However, sorption of acetochlor was most closely correlated to the humic acid carbon, and less to the fulvic acid carbon. The total organic carbon content was found to also significantly influence acetochlor desorption. Discussion  Since the strong linear relationship between the K _d values of acetochlor and the organic carbon content was already released, the corresponding K _oc values were calculated. Considerable variation in the K _oc values suggested that other soil/sediment parameters besides the total soil organic carbon content could be involved in acetochlor sorption. This was revealed by a significant correlation between the K _oc values and the ratio of humic acid carbon to fulvic acid carbon (C_HA/C_FA). Conclusions  When comparing acetochlor sorption in a range of soils and sediments, different K _d values which are strongly correlated to the total organic carbon content were found. Concerning the humus fractions, the humic acid carbon content was strongly correlated to the K _d values, and it is therefore a better predictor of the acetochlor sorption than the total organic carbon content. Variation in the K _oc values was attributed to the differences in distribution of humus components between soils and sediments. Desorption of acetochlor was significantly influenced by total organic carbon content, with a greater organic carbon content reducing desorption. Recommendations and perspectives  This study examined the sorption–desorption processes of acetochlor in soils and sediments. The obtained sorption data are important for qualitative assessment of acetochlor mobility in natural solids, but further studies must be carried out to understand its environmental fate and transport more thoroughly. Although, the total organic carbon content, the humus fractions of the organic matter and the C_HA/C_FA ratio were sufficient predictors of the acetochlor sorption–desorption. Further investigations of the structural and chemical characteristics of humic substances derived from different origins are necessary to more preciously explain differences in acetochlor sorption in the soils and sediments observed in this study.     

Amendment of arsenic and chromium polluted soil from wood preservation by iron residues from water treatment

An iron-rich water treatment residue (WTR) consisting mainly of ferrihydrite was used for immobilization of arsenic and chromium in a soil contaminated by wood preservatives. A leaching batch experiment was conducted using two soils, a highly contaminated soil (1033 mg kg⁻¹ As and 371 mg kg⁻¹ Cr) and slightly contaminated soil (225 mg kg⁻¹ As and 27 mg kg⁻¹ Cr). Compared to an untreated reference soil, amendment with 5% WTR reduced leaching in the highly contaminated soil by 91% for Cr and 98% for As. No aging effect was observed after 103 d. In a small field experiment, soil was mixed with 2.5% WTR in situ. Pore water was extracted during 3 years from the amended soil and a control site. Pore water arsenic concentrations in the amended soil were more than two orders of magnitude lower than in the control for the upper samplers. An increased release of arsenic was observed during winter in both fields, mostly in the deepest samplers. This is likely due to the formation of a pseudo-gley because of precipitation surplus. Stabilization of arsenic and chromium contaminated soil using WTR is a promising method but the transformation of ferrihydrite in soil proves a concern in case of waterlogged soils. Still the amendment minimized the leaching of arsenic, even in cases of seasonal releases.     

Hydroxypropyl-β-cyclodextrin extractability and bioavailability of phenanthrene in humin and humic acid fractions from different soils and sediments

Organic matter (OM) plays a vital role in controlling polycyclic aromatic hydrocarbon (PAH) bioavailability in soils and sediments. In this study, both a hydroxypropyl-β-cyclodextrin (HPCD) extraction test and a biodegradation test were performed to evaluate the bioavailability of phenanthrene in seven different bulk soil/sediment samples and two OM components (humin fractions and humic acid (HA) fractions) separated from these soils/sediments. Results showed that both the extent of HPCD-extractable phenanthrene and the extent of biodegradable phenanthrene in humin fraction were lower than those in the respective HA fraction and source soil/sediment, demonstrating the limited bioavailability of phenanthrene in the humin fraction. For the source soils/sediments and the humin fractions, significant inverse relationships were observed between the sorption capacities for phenanthrene and the amounts of HPCD-extractable or biodegradable phenanthrene (p?<?0.05), suggesting the importance of the sorption capacity in affecting desorption and biodegradation of phenanthrene. Strong linear relationships were observed between the amount of HPCD-extractable phenanthrene and the amount degraded in both the bulk soils/sediments and the humin fractions, with both slopes close to 1. On the other hand, in the case of phenanthrene contained in HA, a poor relationship was observed between the amount of phenanthrene extracted by HPCD and the amount degraded, with the former being much less than the latter. The results revealed the importance of humin fraction in affecting the bioavailability of phenanthrene in the bulk soils/sediments, which would deepen our understanding of the organic matter fractions in affecting desorption and biodegradation of organic pollutants and provide theoretical support for remediation and risk assessment of contaminated soils and sediments.     

Impact of chemical leaching on permeability and cadmium removal from fine-grained soils

The aim of this study was to investigate the influence of chemical leaching on permeability and Cd removal from fine-grained polluted soils. Column leaching experiments were conducted using two types of soils (i.e., artificially Cd-polluted loam and historically polluted silty loam). Chemical agents of CaCl₂, FeCl₃, citric acid, EDTA, rhamnolipid, and deionized water were used to leach Cd from the soils. Results showed that organic agents reduced permeability of both soils, and FeCl₃ reduced permeability of loam soil, compared with inorganic agents and deionized water. Entrapment and deposition of colloids generated from the organic agents and FeCl₃ treatments reduced the soil permeability. The peak Cd effluence from the artificially polluted loam columns was retarded. For the artificially polluted soils treated with EDTA and the historically polluted soils with FeCl₃, Cd precipitates were observed at the bottom after chemical leaching. When Cd was associated with large colloid particles, the reduction of soil permeability caused Cd accumulation in deeper soil. In addition, the slow process of disintegration of soil clay during chemical leaching might result in the retardation of peak Cd effluence. These results suggest the need for caution when using chemical-leaching agents for Cd removal in fine-grained soils.

     

Research and application of method of oxygen isotope of inorganic phosphate in Beijing agricultural soils

Phosphorus (P) in agricultural ecosystems is an essential and limited element for plants and microorganisms. However, environmental problems caused by P accumulation as well as by P loss have become more and more serious. Oxygen isotopes of phosphate can trace the sources, migration, and transformation of P in agricultural soils. In order to use the isotopes of phosphate oxygen, appropriate extraction and purification methods for inorganic phosphate from soils are necessary. Here, we combined two different methods to analyze the oxygen isotopic composition of inorganic phosphate (δ¹⁸O_P) from chemical fertilizers and different fractions (Milli-Q water, 0.5 mol L^?1 NaHCO₃ (pH = 8.5), 0.1 mol L^?1 NaOH and 1 mol L^?1 HCl) of agricultural soils from the Beijing area. The δ¹⁸O_P results of the water extracts and NaHCO₃ extracts in most samples were close to the calculated equilibrium value. These phenomena can be explained by rapid P cycling in soils and the influence of chemical fertilizers. The δ¹⁸O_P value of the water extracts and NaHCO₃ extracts in some soil samples below the equilibrium value may be caused by the hydrolysis of organic P fractions mediated by extracellular enzymes. The δ¹⁸O_P values of the NaOH extracts were above the calculated equilibrium value reflecting the balance state between microbial uptake of phosphate and the release of intracellular phosphate back to the soil. The HCl extracts with the lowest δ¹⁸O_P values and highest phosphate concentrations indicated that the HCl fraction was affected by microbial activity. Hence, these δ¹⁸O_p values likely reflected the oxygen isotopic values of the parent materials. The results suggested that phosphate oxygen isotope analyses could be an effective tool in order to trace phosphate sources, transformation processes, and its utilization by microorganisms in agricultural soils.     

Assessing strategies to mitigate phosphorus leaching from drained clay soils

Assessing mitigation of phosphorus (P) leaching from subsurface drainage systems is challenging due to high spatial and temporal variation in leaching. Mean measured total P leaching from a clayey soil in an eight-year study period (four replicates per treatment) was (kg ha^?1 year^?1): 1.21 from shallow autumn tillage (ShT), 0.84 from unfertilised fallow (UF), 0.81 from conventional autumn ploughing (CT) and 0.57 from structure liming (SL–CT). Treatment was not significant using Richards–Baker flow index or a distance factor as covariate (p = 0.084 and 0.057). A tendency for lower leaching was obtained comparing SL-CT with ShT (p _adjusted = 0.060 and 0.009 respectively). A combination of measures adapted to drainage conditions and clay content in different parts of the field is proposed since P leaching was approximately halved from an adjacent field (4.3 ha) in a three-year post-period compared with a three-year pre-period for structure liming the entire field and drainage system renovation plus structure lime drain backfilling.     

Concentrations,atmospheric partitioning,and air–water/soil surface exchange of polychlorinated dibenzo-p-dioxin and dibenzofuran along the upper reaches of the Haihe River basin,North China

Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDF) were overall measured and compared in ambient air, water, soils, and sediments along the upper reaches of the Haihe River of North China, so as to evaluate their concentrations, profiles, and to understand the processes of gas–particle partitioning and air–water/soil exchange. The following results were obtained: (1) The average concentrations (toxic equivalents, TEQs) of 2,3,7,8-PCDD/PCDF in air, water, sediment, and soil samples were 4,855 fg/m³, 9.5 pg/L, 99.2 pg/g dry weight (dw), and 56.4 pg/g (203 fg TEQ/m³, 0.46 pg TEQ/L, 2.2 pg TEQ/g dw, and 1.3 pg TEQ/g, respectively), respectively. (2) Although OCDF, 1,2,3,4,6,7,8-HpCDF, OCDD, and 1,2,3,4,6,7,8-HpCDD were the dominant congeners among four environmental sinks, obvious discrepancies of these congener and homologue patterns of PCDD/PCDF were observed still. (3) Significant linear correlations for PCDD/PCDF were observed between the gas–particle partition coefficient (K _p) and the subcooled liquid vapor pressure (P _L ⁰) and octanol–air partition coefficient (K _oa). (4) Fugacity fraction values of air–water exchange indicated that most of PCDD/PCDF homologues were dominated by net volatilization from water into air. The low-chlorinated PCDD/PCDF (tetra- to hexa-) presented a strong net volatilization from the soil into air, while high-chlorinated PCDD/PCDF (hepta- to octa-) were mainly close to equilibrium for air–soil exchange.