Measuring the bioavailability of polychlorinated biphenyls to earthworms in soil enriched with biochar or activated carbon using triolein-embedded cellulose acetate membrane

Purpose

Polychlorinated biphenyls (PCBs) are persistent soil contaminants that resist biodegradation and present serious risks to living organisms. The presence of biochar in soils can lower the availability of PCBs to biota. In this study, the effect of biochar enrichment in soils on bioaccumulation of PCBs was investigated.

Materials and methods

We applied two types of biochar including pine needle biochar (PC) and wheat straw biochar (WC), and an activated carbon (AC) to soil (2 % w/w) and employed two alternative methods to quantified rates of bioaccumulation: a living bioassay (using earthworm, Eisenia fetida, as a model organism) and a triolein-embedded cellulose acetate membrane (TECAM).

Results and discussion

Our results show that the application of biochar or AC greatly reduced the uptake of PCBs (particularly less-chlorinated PCBs) by earthworms (the reduction in total PCBs concentration was up to 40.0 and 49.0 % for PC and WC treatments, while 71.6 % for AC application). We found that the bioaccumulation factors (BAFs) for PCBs in the earthworms in biochar/AC-enriched soils were strongly correlated with O:C ratio of the biochar/AC (R ²?=?0.998, p?<?0.05). We observed that BAFs increased at log K _OW below 6.3 and decreased at log K _OW values greater than 6.3. We demonstrated that the concentration of PCBs in TECAM membranes were positively correlated with the concentration of PCBs earthworms in soil.

Conclusions

TECAM offers an efficient and cost-effective method for predicting the bioavailability of PCBs in field-contaminated soils undergoing sorbent-based remediation.

     

Solvent extraction characterization of bioavailability of atrazine residues in soils

Characterization of pesticide bioavailability, particularly in aged soils, is of continued interest because this information is necessary for environmental risk assessment. The objective of this study was to correlate atrazine residue bioavailability in aged soils, as determined by solvent extraction methods, to atrazine mineralization by an atrazine-degrading bacterium. Webster clay loam and Zimmerman fine sand soils were treated with UL-ring-labeled [14C]atrazine and incubated for up to 8 weeks. At the end of each incubation period, soils were either not extracted, extracted with 0.01 M CaCl2, or extracted with 0.01 M CaCl2/aqueous methanol. Soils were then inoculated with the bacterium Pseudomonas sp. strain ADP, which is capable of rapidly mineralizing the atrazine ring. This allowed for the evaluation of the bioavailability of aged atrazine residues without the contribution of atrazine desorption from soil. Results of these studies indicated that the amounts of atrazine residues in aged soils extracted by 0.01 M CaCl2 and aqueous methanol were correlated to amounts of atrazine mineralized by Pseudomonas sp. strain ADP. Consequently, 0.01 M CaCl2/methanol extractable atrazine in aged soils may be used to estimate bioavailable residues, and this technique may be useful to determine the bioavailability of other compounds in soils, especially other triazine herbicides.     

温和提取法评估老化前后土壤中菲的生物有效性

采用温和溶剂提取方法对不同老化时间土壤中的菲进行提取,研究了正丁醇、二氯甲烷、2-羟丙基-β-环糊精(2-Hydroxypropyl-beta cyclodextrin,HPCD)提取量与生物吸收之间的相关性。结果表明,温和有机溶剂(二氯甲烷、正丁醇)提取与温和HPCD提取法对菲的提取量与蚯蚓蓄积量有很好的相关性(p<0.05)。与其他温和试剂提取相比,温和正丁醇提取可以更好地预测菲在土壤中的生物有效性。     

Effect of phosphorus competition on arsenic bioavailability in dry and flooded soils: comparative study using diffusive gradients in thin films and chemical extraction methods

Purpose

Phosphorus influence on arsenic bioavailability in soils and its toxicity to plants is widely recognized. This work compares competitive influence of P on As bioavailability in dry and flooded soils.

Materials and methods

Pot experiments were carried out in dry and flooded soils, respectively. Bioavailable As in soils was measured using diffusive gradients in thin films (DGT), soil solution concentration, and three single chemical extraction methods.

Results and discussion

P concentration at 50 mg/kg promoted wheat growth in dry soil. At concentrations above 50 mg/kg, P competition inhibited wheat growth and enhanced As toxicity. In flooded soil, the rice height and biomass decreased with the increase of P addition. P concentrations above 800 mg/kg were lethal to the rice. The content of As absorbed by wheat and rice roots as well as shoots increased with the increase of P concentration. The bioavailability of As in wheat- and rice-grown soils, determined by all methods, also increased with the increase of P concentration. The correlation analysis between the bioavailable As measured by the all three methods and the content of As in plants showed a significant positive correlation. The Pearson correlation coefficient for the DGT method was higher comparing to all other methods. DGT-induced fluxes in soils (DIFS) modeling further showed sharp decreases of T_c (the characteristic time to reach equilibrium between available solid As pool and soil solution As from DGT perturbation) and increases of desorption and adsorption rate constants (k₁ and k_?1) of As in P-amended soils, reflecting that the kinetic release of As from available solid As pools became much easy from P competition.

Conclusions

P competition in both dry and flooded soils could significantly increase bioavailability of As and further increase its toxicity. Competition effect was more pronounced in flooded soil. DGT is a more accurate method for As bioavailability evaluation in both dry and flooded soils.

     

Estimation of PAH bioavailability to Lepidium sativum using sequential supercritical fluid extraction – a case study with industrial contaminated soils

For the determination of PAH availability to plants a plant accumulation test with Lepidium and sequential supercritical fluid extraction (SSFE) with carbon dioxide as extraction solvent was used, during which the extraction conditions were changed from mild to harsh in order to represent a broad range of potential pollutant-soil interactions. Both approaches were applied in laboratory experiments on industrial contaminated soils which, in addition, were also freshly spiked with PAHs in order to increase the bioavailability. Only Naphthalene, Phenanthrene and, in some cases, Pyrene accumulated from the industrial contaminated soils. Accumulation experiments with spiked industrial soils showed that other PAHs, for example Anthracene, Fluorene and even high weight PAHs like Benzo(a)pyrene, also could be taken up by plants. SSFE extraction data were compared to accumulated amounts of PAHs in the plants. Strong correlations were found for Phenanthrene between plant accumulation and extractability under very mild extraction conditions. For Naphthalene, accumulation did not correlate with its extractability in the industrial soils. The possibility exists that bioavailability in soil was eclipsed by an accumulation in the gas phase due to the high volatility of Naphthalene. Supercritical fluid extraction appears to be a promising tool to estimate Phenanthrene availability to plants, but further studies for the evaluation of other PAHs are recommended. This could be helpful for the determination of the feasibility of phytoremediation applications on industrially contaminated soils.     

Homogeneous preparation of cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB) from sugarcane bagasse cellulose in ionic liquid

Cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) were prepared homogeneously in a 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid system from sugarcane bagasse (SB). The reaction temperature, reaction time, and molar ratio of butyric (propionic) anhydride/anhydroglucose units in the cellulose affect the butyryl (B) or propionyl (P) content of CAB or CAP samples. The (13)C NMR data revealed the distribution of the substituents of CAB and CAP. The thermal stability of sugar cane bagasse cellulose was found by thermogravimetric analysis to have decreased after chemical modification. After reaction, the ionic liquid was effectively recycled and reused. This study provides a new way for high-value-added utilization of SB and realizing the objective of turning waste into wealth.     

Spatial distribution of roots and cracks in soils cultivated with sunflower

The aim of this research was to investigate the spatial distribution of roots and cracks in two clay soils cropped with sunflower under different inter-row spacing in order to identify the optimal management. A latin square experimental design was applied to compare bare soil and soil cropped with sunflower, with three plant densities, obtained by keeping constant the number of plants on the row (3 plants m^?1) and varying the row spacing (0.4, 0.6, 0.8 m). The presence of the crop and the different distance between rows influenced soil moisture content as well as the root spatial distribution and thus the structural features of cracks. Increasingly lower values of moisture were found in both soils as the distance between rows decreased; an opposite trend was observed for both root density and crack size. The volume of cracks in the soil grown with sunflower at 0.4 m row spacing was 201.4 m³ ha^?1, thus 8 times higher than the value on the bare soil and 2.5 times higher compared to the one grown at 0.8 m between rows. Optimal results in terms of root density, soil moisture and crack size were obtained with an inter-row spacing of 0.6 m.     

Ageing of vanadium in soils and consequences for bioavailability

Total vanadium (V) concentrations in soils commonly range from 20 to 120 mg kg^?1. Vanadium added directly to soils is more soluble than geogenic V and can be phytotoxic at doses within this range of background concentrations. However, it is unknown how slow sorption reactions change the fate and effect of added V in soils. This study addresses the changes in V solubility, toxicity and bioavailability in soils over time. Four soils were amended with pentavalent V in the form of a soluble vanadate salt, and extractable V concentrations were monitored over 100 days. The toxicity to barley and tomato plants was evaluated in freshly spiked soils and in the corresponding aged soils that were equilibrated for up to 330 days after spiking. The V concentrations in 0.01 m CaCl₂ soil extracts decreased approximately two‐fold between 14 and 100 days after soil spiking, and the reaction kinetics were similar for all soils. The phytotoxicity of added V decreased on average two‐fold between freshly spiked and aged soils. The reduced toxicity was associated with a corresponding decrease in V concentrations in the isolated soil solutions and in the shoots. The V speciation in the soil solution of the aged soils was dominated by V(V); less than 8% was present as V(IV). Oxalate extractions suggest that the V(V) added to soils is predominantly sorbed onto poorly crystalline oxyhydroxides. It is concluded that the toxicity of V measured in freshly spiked soils may not be representative of soils subject to a long‐term V contamination in the field.     

Chemical extraction to assess the bioavailability of chlorobenzenes in soil with different aging periods

Purpose  

Bioavailability is mainly influenced by aging and desorption of contaminants in soil. The purpose of this study was to investigate the desorption kinetics of chlorobenzenes (CBs) in soil and to investigate whether chemical extractions are suitable for the bioavailability assessment of CBs in soil.     

A comparison of 5 soil phosphorus extraction methods applied to different soils of South of Iran

Phosphorus (P) fertilization is commonly based on soil testing, for which a variety of different soil P extraction methods are in use. In this research, the correlation and calibration of five extraction techniques for available P were studied: Soltanpour and Schwab, Olsen, EDTA-Na₂, Paauw and Morgan in 168 different soil samples from 63000 ha of Sirjan pistachio orchards of Kerman province, Iran. The Morgan reagent extracted the most P and then EDTA-Na₂> Olsen> Soltanpour and Schwab> Paauw extracted more phosphorus, respectively. Positive and significant correlation (P < 0.05) existed among all extractants. The correlation coefficients between different extractants and plant P concentration indicated that, EDTA-Na₂ (P < 0.01), Olsen and Paauw methods (P < 0.05) had positive and significant correlation with leaf P concentration and thus with due attention to acceptable relationship with plant indices, the Olsen and EDTA-Na₂ methods could be used to advise on available P.     

Disputable issues in interpreting the results of chemical extraction of iron compounds from soils

In Russia, iron is chemically fractionated according to a parallel scheme. Pyrophosphate-soluble iron (Fe_pyr) is considered to participate in organomineral complexes, oxalate-soluble iron (Fe_ox) is believed to enter amorphous + poorly crystallized compounds, and dithionite-soluble iron (Fe_dit) is meant to represent the free (nonsilicate) compounds. However, the investigations prove that the commonly used subtraction operations (Fe_ox ? Fe_pyr) and (Fe_dit ? Fe_ox) are invalid because of the nonadditive action of the reagents in the parallel scheme of extraction. The low selectivity of reagents requires a new interpretation of chemically extracted iron compounds. In automorphic soils, the content of oxalate-soluble iron should be interpreted as the amount of Fe(III) capable of complexing with organic ligands; in hydromorphic soils with a stagnant moisture regime, it should be interpreted as the amount of iron (III) capable of being reduced in a short time. The content of dithionite-soluble compounds should be regarded as the amount of iron (III) within both (hydr)oxides and silicates potentially prone to reduction.     

Colonization of wheat roots by Gaeumannomyces graminis inhibited by specific soils,microorganisms and ammonium-nitrogen

Lineal extension of Gaeumannomyces graminis var. tritici hyphae along roots of intact wheat plants growing in soils was measured. Hyphal growth rates were lower in soils treated with NH₄⁺-N than with NO₃^?-N. In a soil that is suppressive to the take-all disease, the controlling influence of NH₄⁺-N was eliminated by soil fumigation (methyl bromide), and reintroduced to fumigated soil by additions of 1% nonsterile soil. Effects of fumigation on hyphal growth were absent in a nonsuppressive soil, and in NO₃^?-treatments of the suppressive soil. When inocula of selected groups of wheat rhizoplane microflora were reintroduced into a fumigated or a soil-reinoculated soil via a root-food base, the Pseudomonas spp. consistently appeared more suppressive in NH₄⁺-N treatments than the general bacterial flora, Bacillus spp. spores, streptomycetes, and fungi.     

Bacterial diversity in soils subjected to long-term chemical fertilization can be more stably maintained with the addition of livestock manure than wheat straw

Addition of organic matter such as livestock manures and plant residues is a feasible practice to mitigate soil degradation caused by long-term application of chemical fertilizers, and the mitigation is largely mediated though activities of the soil-dwelling microorganisms. However, the roles of different kinds of organic matter in maintaining bacterial community structure have not been assessed in a comparative manner. In this study, 454 pyrosequencing of 16S rRNA gene was employed to compare the bacterial community structure among soils that had been subjected to 30 years of NPK fertilization under six treatment regimes: non-fertilization control, fertilization only, and fertilization combined with the use of pig manure, cow manure or low- and high-level of wheat straws. Consistent with expectation, long-term application of NPK chemical fertilizers caused a significant decrease of bacterial diversity in terms of species richness (i.e. number of unique operational taxonomic units (OTU)), Faith's index of phylogenetic diversity and Chao 1 index. Incorporation of wheat straw into soil produced little effects on bacterial community, whereas addition of either pig manure or cow manure restored bacterial diversity to levels that are comparable to that of the non-fertilization control. Moreover, bacterial abundance determined by quantitative PCR was positively correlated with the nutritional status of the soil (e.g., nitrate, total nitrogen, total carbon, available phosphorus); however, bacterial diversity was predominantly determined by soil pH. Together, our data implicate the role of livestock manures in preventing the loss of bacterial diversity during long-term chemical fertilization, and highlight pH as the major deterministic factor for soil bacterial community structure.     

A comparison of extraction procedures for water‐extractable organic matter in soils

The characteristics of dissolved organic matter (DOM) in soils are often determined through laboratory experiments. Many different protocols can be used to extract organic matter from soil. In this study, we used five air‐dried soils to compare three extraction methods for water‐extractable organic matter (WEOM) as follows: (i) pressurised hot‐water‐extractable organic carbon (PH‐WEOC), a percolation at high pressure and temperature; (ii) water‐extractable organic carbon (WEOC), a 1‐hour end‐over shaking; and (iii) leaching‐extractable organic carbon (LEOC), a leaching of soil columns at ambient conditions. We quantified the extraction yield of organic carbon; the quality of WEOM was characterized by UV absorbance, potential biodegradability (48‐day incubation) and parallel factor analysis (PARAFAC) modelling of fluorescence excitation emission matrices (FEEMs). Biodegradation of dissolved organic carbon (DOC) was described by two pools of organic C. The proportions of labile and stable DOC pools differed only slightly between the WEOC and LEOC methods, while PH‐WEOC contains more stable DOC. The mineralization rate constants of both labile and stable DOC pools were similar for the three methods. The FEEMs were decomposed into three components: two humic‐like fluorophores and a tryptophan‐like fluorophore. The effect of extraction method was poorly discriminant and the most similar procedures were PH‐WEOC and LEOC while WEOC extracts were depleted in humic‐like fluorophores. This study demonstrates that WEOM quality is primarily determined by soil characteristics and that the extraction method has a smaller, but still significant, impact on WEOM quality. Furthermore, we observed considerable interaction between extraction procedure and soil type, showing that method‐induced differences in WEOM quality vary with soil characteristics.     

长期施用堆肥对小麦根际及非根际土壤化学性质的影响

Compost of different rates was applied to artificial field plots of a low humic andosol at National Agriculture Research Center (NARC)of Japan for 15 or 28 years,and their effects on the chemical properties of wheat rhizosphere soil and nonrhizosphere soil were measured.Contiuous application of compost for 28 years resulted in raise of soil C,N,P,pH and exchangeable based.The building up of compost for 28 years resulted in raise of soil C,N,P,pH and exchangeale bases,The building up of organic matter in the soil occureed slowly.A residual effect of the compost on soil chemical properties was still present after 13 years of no application,but this effect was weaker in comparison with that of the continuous application treatments.In the rhizosphere soil,NaHCO3-extracted P and exchangeable Ca were higher than those in the bulk soil.The removal of free organic acid slightly affected the soil pH,especially,the rhizosphere soil pH.The raise of soil pH may result from the increase of exchangeable base by the application of compost.     

Population dynamics of amoebae in soils suppressive and non-suppressive to wheat take-all

Populations of soil amoebae were estimated throughout two wheat crops and a fallow from wheat rotations suppressive and non-suppressive to take-all. The suppressive pasture-pasture-wheat plot showed higher rhizosphere populations of mycophagous amoebae and higher associations of mycophagous and other amoebae with wheat roots throughout the crop period than the non-suppressive continuous-wheat plot. Populations of mycophagous amoebae were positively and significantly (P = 0.05) correlated with populations of the take-all fungus in both soils, and with soil moisture in the non-suppressive soil. The possible role of mycophagous amoebae in the wheat rhizosphere in suppressive soil is discussed.     

Fumonisin production and bioavailability to maize seedlings grown from seeds inoculated with Fusarium verticillioides and grown in natural soils

The fungus Fusarium verticillioides infects maize and produces fumonisins. The purpose of this study was to determine the ability of F. verticillioides to produce fumonisins in synthetic and natural soils and their biological availability to maize roots. Maize seeds were inoculated with a pathogenic strain of F. verticillioides (MRC826) and planted in synthetic and three different natural soils. There were statistically significant reductions in stalk weight and root mass and increased leaf lesions in the MRC826-treated seedlings in all soil types. Fumonisins were detected in all of the soils of seedlings grown from MRC826-inoculated seeds. The fumonisin produced in the soils was biologically available to seedlings as demonstrated by the statistically significant elevation of free sphingoid bases and sphingoid base 1-phosphates in their roots. These results indicate that F. verticillioides produced fumonisins in the autoclaved synthetic and natural soils and that the fumonisin produced is biologically available on the basis of evidence of inhibition of ceramide synthase.     

Depth distribution and bioavailability of pollutants in long-term differently tilled soils

Pollutants can be introduced to soil through the application of organic and inorganic fertilizers and pesticides and through atmospheric depositions. The objective of this research was to evaluate the influence of long-term (9–17 years) tillage systems on the behavior of pollutants in soils. Bioavailability and enrichment of heavy metals, arsenic, and organics, i.e. polychlorinated biphenyls (PCB’s) and a chlorinated phenol (2,4-DCP) were measured in a Eutric Cambisol and a Luvisol under conventional tillage (CT), reduced tillage (RT), and no-tillage (NT). Soil samples were collected from 0 to 3, 3 to 10, and 10 to 25 cm depths.

The upper layer of NT soils was enriched in pollutants, but concentrations decreased with increasing soil depth. Atmospheric deposition of pollutants and input via organic fertilizers was noticeable in soils under long-term NT. Total amount of zinc (59 mg kg⁻¹) was significantly enriched in the 0–3 cm depth of the Luvisol under NT and this was attributed to higher sorption capacity for heavy metal input via liquid manure. In the Eutric Cambisol, NT resulted in significant increase of cadmium extracted by aqua regia in the arable layer of 0–25 cm. As a result of higher soil organic C, long-term accumulation of PCB’s in NT soils was more pronounced than in plowed soils. In plowed soils the mixing effect resulted in homogeneous distribution of pollutants within a soil depth of 0–25 cm.

The enrichment of organic C in RT and NT soils emphasizes the role of soils as a sink for pollutants, buffering the contaminants against leaching and transfer into crops.     

Regression equations to monitor inorganic nitrogen changes in fallow and wheat soils

Soil NH⁺₄-N and NO^?₃-N at five soil depths (0–10, 10–20, 20–40, 40–60, 60–80 cm) and some environmental variables were measured in a field trial under fallow and wheat for 9 months.Significant linear and quadratic relationships were obtained relating soil NH⁺₄-N, NO^?₃-N, NH⁺₄-N + NO^?₃-N, and NH⁺₄-N + NO^?₃ + total-N uptake by wheat to soil heat accumulation (temperature), moisture, and rainfall. R² values generally decreased with soil depth and the maximum value (37%) was obtained for NO^?₃-N changes in the topsoil (0–10 cm).Although a considerable amount of variation in the inorganic values recorded is not included in the equations, our results suggest that the development of the above relationships particularly of the quadratic type are useful to predict crop requirements for N by measurement of environmental variables in the field.