Current and Future Outlook of Dredged and Sewage Sludge Materials in Agriculture and Environment (3 pp)

-  In the late 1960’s there was an increasing realization in the U.S.A. and other parts of the world, especially in Europe of the potential problems associated with the disposal of spoil and sewage sludge materials. While insufficient information was available to determine potential adverse effects of disposal on land, many people including those in the scientific community had articulated their objections on the use of these materials in agriculture because data do not provide adequate environmental protection information. In many cases, site-specific geochemical and biological factors are typically excluded from the decision process (Wenning and Woltering 2001). Because of continued studies and far-reaching research during the last 40 years on the environmental effects of dredged and sludge materials, the scientific community and regulatory agencies in the U.S.A. are now in a much better position to appraise the environmental and possible agricultural impacts connected with the disposal of dredged and sludge materials by diverse disposal methods.     

The role of sediment-feeding oligochaeteTubifex on the availability of trace metals in sediment pore waters as determined by diffusive gradients in thin films (DGT)

Background  Available fractions of metal concentrations in sediment pore water are difficult to measure without disturbing the sediment core. The available fraction is an important parameter in understanding the risks for benthic organisms. Not much is known about the influence of the presence of benthic organisms to the available fraction. Objectives  The aim of this study was to discuss the dynamics of metal behaviour in natural sediments and the influence of the presence ofTubifex on sediment chemistry using DGT. Methods. DGT-probes were added to six beakers to cover a depth profile of 0 to 13 cm. The six beakers contained three different sediments. For each sediment, one beaker had 1 g ofTubifex added, the other beaker contained noTubifex. After two weeks of exposure, the probes were withdrawn and strips were analysed for their content of cadmium, copper and zinc. Results and discussion  Available concentrations were higher in the upper layer (0–1 cm) of the sediment core, where conditions are generally more oxic. The presence ofTubifex worms led to a decrease of the available concentrations in the upper layer, due to the competition of the worms with the DGT for the available metal fraction. On the other hand, the presence of the worms led, via bioturbation, to an increased oxygen penetration depth in the sediment, and, as a consequence, to an increase of the available fraction in the next-higher sediment layer. Conclusions  In sediment cores without organisms, very steep gradients of the available metal concentration in pore water have been found. The change from a high to low amount of available fraction corresponds to the change from oxidised conditions in the surficial sediment layer to reduced conditions in the lower sediment layers. The tunnelling behaviour ofTubifex worms leads to a penetration of oxygen to deeper sediment layers, and to an increase of the available metal fraction in the pore water.Tubifex competes with DGT for the available fraction, resulting in lower metal amounts accumulated in the DGT probe. Competition is the prevailing effect in the top 1 cm layer of all sediments. In the second 1 cm layer, competition, in most cases, is not strong enough to compensate the increase in metal availability due to the broadening of the oxidised zone. Recommendations  The effects of sediment organisms on the deepening of the oxidised layer and on the availability of metals in pore water need further investigations and quantification. DGT is recommended as an instrument for measuring available metal concentrations in these studies.     

Confined disposal facility characterization for beneficial reuse of dredged material: a case study to demonstrate a structured approach to sampling and data analysis

Purpose  

Confined disposal facilities (CDFs) are widely used for disposal of navigation dredged material, but many are running out of capacity. Removal of dredged material for beneficial use offers potential for sustainable operations, but requires characterization with a high degree of confidence. Few data are available to inform characterization efforts in these artificial depositional environments; thus, a CDF case study was used to demonstrate a structured approach to sampling and data analysis.     

Prognosis of Methane Formation by River Sediments (9 pp)

Background   Under anoxic conditions typically prevailing in disposal sites for dredged sediment, methanogenesis is the terminal step during microbial degradation of sediment organic matter. Sediment gas production may pose several problems to site management and post-closure utilisation. Depending on the magnitude of gas/methane formation and the intended utilisation of the site, countermeasures will have to be effected during and after deposition of the dredged material. For this purpose it may be of interest to pre-estimate the extent of gas formation from simple sediment variables. Therefore, the aim of the investigations presented here was to analyse the interrelations between gas formation and sediment physical, chemical and biological qualities. Methods   Freshly sampled riverbed sediment from nine German federal waterways was analysed for standard solid physical and chemical parameters, pore water composition, cell counts of methanogenic and sulfate-reducing bacteria, and gas formation over a period of 500 days. Particle size and density fractionation were carried out in order to characterise organic matter quality. Correlations between methane formation and sediment chemical, physical and microbiological characteristics were tested using linear and multiple correlation analysis. Results and Discussion   The selected sediments, including two with marine influence, differed strongly regarding texture, chemical parameters, pore water composition, and methanogen cell counts. The course of methane formation was found to follow distinct phases. The commencement of methane formation was preceded by a lag phase of variable duration. The lag phase was followed by a strong increase of the methane formation rate up to a sediment-characteristic maximum of 5–30 nmol CH4 h–1 g dw–1. Eventually, the rate of methane formation decreased and reached a more stable, long-term level. The extent and amplitude of each phase varied strongly between sediments and could be correlated well with only a few standard analytical parameters, despite the strong heterogeneity of sediment with respect to chemical, physical, and biological characteristics. Lag phase duration depended strongly on the content of inorganic electron acceptors and also on the number of methanogens present at the beginning of the experiment. Maximum and steady state methanogenesis were mainly determined by sediment total nitrogen. As analysis of sediment density fractions revealed that total nitrogen reflected the share of readily degradable macroorganic matter. Conclusion and Outlook   The results imply that the observed methane formation is a function of the temporally changing balance of the availability of electron acceptors and H2, and the share of easily degradable organic matter. For fresh riverbed sediments, the latter may be deduced from total nitrogen content. Overall, the results showed that methane formation by freshly dredged material may well be pre-estimated from standard analytical data within the first few years of deposition. However, the differently degradable organic matter pools will change over time with respect to size, chemical nature and association with the sediment mineral phase. It can thus be expected that the correlations found in this study will not be readily transferable to older materials. Further studies on the gas formation and organic matter quality by older sediments, e.g. from older dredged material disposal sites of known age, should be conducted and results should be combined with existing organic matter degradation models in order to improve the prediction of sediment gas formation over time.     

Ripening of clayey dredged sediments during temporary upland disposal a bioremediation technique

Background and Goal  In the Netherlands about 40 million m³ of sediment has to be dredged annually for both maintenance and environmental reasons. Temporary upland disposal is the most widely adopted alternative for dredged sediments worldwide. For good management of temporary disposal sites, knowledge is needed on the processes controlling the behavior of the sediments during disposal. Therefore, a review of the literature was made to get an integrated overview about processes that take place during temporary disposal. Ripening  After disposal of clayey sediments, the following spontaneous dewatering processes can be distinguished: sedimentation, consolidation, and ripening. Sedimentation and consolidation are relatively fast processes, whereas ripening can take up to several years. In a remediation perspective, the ripening of sediments is the most important dewatering process. Ripening, which may be subdivided into physical, chemical, and biological ripening, transforms sediment into soil. Physical ripening is the irteversible toss of water and results in the formation of soil prisms separated by shrinkage cracks. Continuing water loss causes a breaking up of the prisms into aggregates. The aggregates produced by this ongoing desiccation process usually remain quite large (>50 mm) and can only be further broken down by weathering processes like wetting and drying or by tillage. As a result of the aeration caused by physical ripening, also chemical and biological ripening take place. Chemical ripening can be defined as the changes in chemical composition due to oxidation reactions and leaching of soluble substances. Biological ripening is the result of the activity of all kinds of soil fauna and flora that develop as a result of aeration, including both the larger and the microscopic forms of life. Decomposition and mineralization of soil organic matter caused by micro-organisms can be seen as the most important aspect of biological ripening. Many interactions exist between the different ripening processes. Conclusions and Outlook  Oxygenation of the dredged sediment is improved as a result of the natural ripening processes: the air-filled porosity increases, the aggregate size decreases, and the initially high respiration rates caused by chemical and biological ripening decreases. Therefore, conditions in the disposal site become more favorable for aerobic biodegradation of organic pollutants like Polycyclic Aromatic Hydrocarbons (PAH) and mineral oil. It is concluded that the naturally occurring process of ripening can be used as a bioremediation technique. Ripening in an upland disposal site is an off-site technique, and therefore, the process could be enhanced by means of technological interference. However, it is concluded that the knowledge currently available about upland disposal is not sufficient to distinguish critical process steps during the ripening and bioremediation of PAH and mineral oil polluted sediments because of the complex relationships between the different ripening processes and bioremediation.     

The ability of the DGT soil phosphorus test to predict pasture response in Australian pasture soils – a preliminary assessment

Diffusive gradients in thin‐films (DGT) technology provides an alternative assessment of available phosphorus (P) for a range of crops, suggesting a preliminary examination of the performance of the new DGT‐P test, compared to existing bicarbonate extractable Olsen and Colwell P tests, for pastures is justified. This study utilized historic data from the Australian National Reactive Phosphate Rock (NRPR) study (1992–1994) that included 25 experimental sites representing a wide range of soil types and climates used for pasture production. Stored (~19 yr) soil samples were analysed for DGT‐P, Olsen P and a single point P buffering index (PBI) and re‐analysed for Colwell P. Results showed the traditional bicarbonate extractable Colwell (r² = 0.45, P < 0.001) and Olsen P (r² = 0.27, P < 0.001) methods predicted relative pasture P response more accurately, compared to the novel DGT‐P test (r² = 0.09, P = 0.03) when all 3 yr of data were examined. We hypothesize that the harsher bicarbonate extraction used for the Olsen and Colwell methods more accurately reflects the ability of perennial pasture roots to access less labile forms of P, in contrast to the DGT‐P test, which does not change the soil pH or dilute the soil and appears unable to fully account for a plants ability to solubilize P. Further studies are needed to compare the capacity of DGT‐P to measure P availability in perennial pasture systems and to better understand the soil chemical differences between pasture and cropping systems.     

Lab-scale feasibility tests for sediment treatment using different physico-chemical techniques

Purpose  

The fairly high amounts of sediments dredged in coastal or internal water bodies for navigational and/or environmental purposes claims for the identification of appropriate management strategies. Dredged sediments are frequently affected by organic and inorganic contamination, so that their reuse, as an alternative to final landfill disposal, could need remediation. In this framework, a two-year joint research project was carried out to assess the feasibility of different remediation technologies for the treatment of polluted sediments.     

A Study of Diffusive Gradients in Thin Films for the Chemical Speciation of Zn(II), Cd(II), Pb(II), and Cu(II): The Role of Kinetics

The lability and mobility of Zn(II)–, Cd(II)–, Pb(II)–, and Cu(II)–humic acid complexes were studied using diffusive gradients in thin films (DGT). A unique feature of this research was (1) the use of DGTs with diffusive layer thicknesses ranging from 0.4 to 2.0 mm to study lability and mobility of Zn(II)–, Cd(II)–, Pb(II)–, and Cu(II)–humic acid complexes, combined with (2) the application of a competing ligand exchange (CLE) method using Chelex 100, the same chelating resin that is used in DGT, to study the kinetic speciation. The CLE experiments were run immediately after the completion of the DGT experiments, thereby allowing effects of the competing ligand to be separated from the effects introduced by the use of the polyacrylamide gel that is used in DGT. The results indicate that Zn(II) and Cd(II) tend to form more labile and more mobile complexes with humic acid than Pb(II) or Cu(II). The dissociation rate constants of Zn(II), Cd(II), and Pb(II) were found to increase with the ionic potential of the metal, suggesting that the binding between some trace metals and humic acid has a significant covalent component. Furthermore, the results suggest that the Eigen mechanism may not be strictly obeyed for metals such as Cu(II) which have high rate constants of water exchange, k _w. Consequently, the markedly slow kinetics of Cu(II)-HA species suggests that the usual equilibrium assumption may not be valid in freshwaters.     

Freely dissolved PCDD/F concentrations in the Frierfjord,Norway: comparing equilibrium passive sampling with “active” water sampling

Introduction  

Equilibrium passive samplers consisting of 55-μm polyoxymethylene (POM) and 170-μm polydimethylsiloxane were tested for the analysis of polychlorinated dibenzodioxin/furan (PCDD/F) in the pore water and overlying water of the Frierfjord, a bay in southern Norway. This fjord is heavily polluted with PCDD/Fs due to emissions from a former Mg smelter.     

Biological effects-based sediment quality in ecological risk assessment for European waters

An overview is given of decision making frameworks for Ecological Risk Assessment (ERA) used for sediment in a number of European countries. These frameworks fall into two categories:

沉积物中重金属铜的解吸动力学模拟

采用DIFS模型模拟了DGT在沉积物中放置过程中,吸附态铜从固相解吸的动力学过程。结果表明,对于模拟的三个样品,R值均小于1,均属于部分补给情况(固相的补给不能使DGT界面处孔隙水浓度维持在初始水平)。对于R值为0.74的M1样品,Kd值较高,解吸速率常数k-1较大,在DGT放置时间T内,吸附态铜可以迅速解吸并补给DGT的消耗,DGT界面处孔隙水Cu浓度基本维持在一个稳定的值,但低于初始浓度,吸附态铜的消耗范围较小(<0.15 cm);对于M2和M3样品,R值、Kd和k-1均小于M1,固相的补给很小,DGT界面处孔隙水浓度随着放置时间的增加而降低,且吸附态铜的消耗范围也较大。由模拟结果可知,沉积物中重金属释放动力学过程受到生物有效态铜的容量和解吸动力学参数共同影响。对于稳定状态部分补给的情况(M1样品),典型特征是较高的Kd和适中的k-1;而对于非稳定态部分补给的情况(M2和M3样品),典型特征是较低的Kd值和适中或者较高的k-1。     

Effects of humic acids from vermicomposts on plant growth

The interactions between earthworms and microorganisms can produce significant quantities of plant growth hormones and humic acids which act as plant regulators. Experiments were designed to evaluate the effects of humic acids extracted from vermicompost and compare them with the action of commercial humic acid in combination with a commercial plant growth hormone, indole acetic acid (IAA) which is a commonly found in vermicomposts. In the first experiments, humic acids were extracted from cattle, food and paper waste vermicomposts. They were applied to a plant growth medium, Metro-Mix360 (MM360), at rates of 0, 250 or 500 mg humates kg⁻¹ dry wt. of MM360, to marigold, pepper, and strawberry plants in the greenhouse. Substitution of humates ranging from 250 to 1000 mg kg⁻¹ MM360 increased the growth of marigold and pepper roots, and increased the growth of roots and numbers of fruits of strawberries significantly. In other experiments, humic acids extracted from food waste vermicomposts were applied at a rate of 500 mg kg⁻¹ dry wt. of MM360, singly or in combination with IAA at a rate of 10⁻⁵ μM, to pepper seedlings. This experiment was designed to compare the differences in effects between the most effective dosage rate of humic acid from food waste, a phytohormone (IAA), and a commercial source of humic acid. The numbers of pepper flowers and fruits increased significantly in response to treatment with humic acid, IAA and a combination of humic acid and IAA. Peppers treated with humic acids extracted from food waste vermicomposts produced significantly more fruits and flowers than those treated with commercially-produced humic acids.     

Monitoring Metal Speciation in The rivers Meuse and Rhine Using DGT

Although a number of metal speciation methods are nowadays available, most water quality regulations are based on total metal concentrations. One of the main reasons for the ignorance of speciation is the lack of methods with potentiality for monitoring. Conditions that have to be met by such speciation methods are: simple performance, robust and sufficiently accurate. In this study the potential for monitoring purposes of Diffusive Gradients in Thin films (DGT) is investigated as part of a European project for sensor development for routine prediction of metal biouptake in natural waters. Performance characteristics of DGT have been assessed in experiments under controlled laboratory conditions and during in situ application over 4–9 months under different hydrological conditions in the rivers Meuse and Rhine. Results have been worked out for Cu, Ni and Pb. The study shows that DGT has sufficient potential as a robust tool in routine monitoring to observe trends in water quality. However, it appears that during in situ application of DGT the measurement uncertainty of the results is much larger than under laboratory conditions. The increase in measurement uncertainties will partially be due to uncertainties in some as constant considered factors in the calculation of the DGT concentration. For Cu and Ni, the average values for the reproducibility in the rivers Meuse and Rhine appeared to be 28% and 17%, respectively, whereas under laboratory conditions the reproducibilities for both metals were better than 10%. In the speciation of Cu, Ni and Pb in the rivers Meuse and Rhine, the labile fraction, determined using DGT, decreased in the series Ni, Cu, Pb. The ratio of the non-labile and labile fractions of the metals appeared to decrease with increasing content of Dissolved Organic Carbon (DOC).     

The Monitoring of Cr(III) and Cr(VI) in Natural Water and Synthetic Solutions: An Assessment of the Performance of the Dgt and Dpc Methods

The technique of diffusive gradients in thin films or diffusive gradient in thin films (DGT) has been used in this work for the in situ measurement of labile Cr(III) and Cr(VI) species. Direct measurement of Cr(VI) was also carried out in parallel with a field-based colourimetric technique based on the EPA 7196 diphenyl-carbohydrazide (DPC) method. The efficiency of the DGT and DPC methods were tested (a) in the laboratory, using synthetic solutions in the presence of realistic concentrations of Cr, humic substances (HS), and ethylenediaminetetraacetic acid (EDTA), and (b) in the field, in river water affected by effluents discharged by the tannery industry. The main advantage of the DGT method is that it allows the in situ separation of labile species of Cr(III) and Cr(VI), though there are still uncertainties about its performance in field conditions. The DPC method proved to be a fast, accurate, and relatively economical option for the field-based determination of Cr(VI). Sample acidification and ageing of unacidified samples from contaminated aquatic environments, produced significant errors in the determination of ‘dissolved’ Cr. The concentration of Cr(VI) determined by either the DGT or the DPC method exceeds recommended international guidelines.     

TBT-contaminated Sediments: Treatment in a Pilot Scale (9 pp)

-  Dedicated to Prof. Dr. Ulrich Förstner on his 65th birthdayBackground, Aims and Scope   Sediments in harbours and nearby shipyards demonstrate widespread contamination with tributyltin (TBT). Therefore, reuse and relocation of dredged material from these locations are prohibited. Even if the International Marine Organization (IMO) convention concerning TBT-based paints is ratified (Champ, 2003) the TBT problem in sediments will continue to remain for many years due to the persistence of TBT. Methods   An electrochemical process has been developed to treat polluted sediments. Dredged materials with high and low TBT-contents were studied on a technical and a pilot scale. The treatment process was assessed by chemical analysis and a biotest battery. Additionally, an economic analysis was performed to check the economic feasibility of the process to treat dredged material from two different locations at different operating conditions. Furthermore an up-scaling estimation was performed to evaluate treatment costs at a larger scale, i.e. for a plant having a capacity of 720 000 t/a.Results and Discussion   Butyltin species and polycyclic aromatic hydrocarbons (PAH) were decomposed due to electrochemically-induced oxidation, while the treatment did not alter heavy metal and PCB concentrations. The bacteria luminescence test indicated a reduced toxicity after the electrochemical treatment, while the algae growth inhibition test and bacteria contact test did not confirm these results. Based on a small consumer price of €0.12/kWh, treating the high-contaminated sediment in the pilot plant would cost €21/m³ and €31/m³ for the low contaminated sediment, respectively. Assuming an industrial consumer price of €0.06/kWh for electricity in an up-scaled process with a capacity of 720 000t/a, the total treatment costs for the low contaminated sediment would be €13/m³. Conclusion   The results of treating dredged material from Bremerhaven and the fine-grained fraction from the METHA plant show that the effectiveness of the process performance is more related to the binding form and sediment composition than to the initial concentration of TBT. The electrochemically treated material complies with chemical criteria for relocation of dredged material, but post-treatment, e.g. washing and/or reduction of remaining oxidants with Fe-II-salts, is needed to fulfil ecotoxicological criteria for relocation. Economic investigations have shown that the electrochemical treatment might be a technical option to treat TBT contaminated, dredged material. However, the technique is not fully developed and cannot remove all chemicals of concern, e.g. heavy metals. The decision as to whether this technique can be applied is site-specific and should be taken based on the case-by-case approach.Recommendation and Outlook   Since biotests integrate the effects of all contaminants present in a sample, process-accompanying evaluation procedures need additional assessment methods such as TIE (toxicity identification evaluation) as a second tier following ecotoxicological tests, in which the reasons for the effects are identified. For reasons of sustainability, a much more effect-oriented and long-term cost effective approach should be applied in future to avoid the release of harmful substances into the environment. Life cycle assessment should be carried out to identify and quantify impacts of sediment treatment processes in order to take into account both the distant effects of local actions and local effects of distant actions.     

Evaluating the mercury distribution and release risks in sediments using high-resolution technology in Nansi Lake,China

Purpose

Mercury (Hg) and methylmercury (MeHg) are easily released from sediments to overlying water and cause secondary contamination. In general, Hg concentrations are low in natural aquatic environments, but Hg toxicity is high. Therefore, it is important to assess the mobility and release risks of Hg and MeHg from surface sediment using in situ high-resolution sampling techniques.

Methods

The profile distribution of Hg and MeHg was obtained for samples from Weishan sub-lake (WL) and Dushan sub-lake (DL) of Nansi Lake, China, by high-resolution dialysis (HR-Peeper probes) and the diffusive gradients in thin films (DGT) technique at mm-resolution. Furthermore, Hg mobility and release risks in sediments were evaluated by combining BCR (European Community Reference Bureau) extraction and DGT-measured data.

Results

The soluble concentrations of Hg in surface sediments in WL and DL were 21.70 and 19.38 ng L^?1 and the DGT-labile concentration of Hg were 8.21 and 10.30 ng L^?1, respectively. The soluble and labile Hg and MeHg concentrations were higher in the surface sediments (from??40 to 0 mm) than in deep sediments. The distribution of the labile-Hg was controlled by the ferrimanganic (hydr)oxide and total nitrogen rather than organic carbon content. The non-residual components accounted for a greater proportion of the interface, which further confirmed Hg was more active on the surface layer of the sediment. The resupply ability indicated that the release of Hg from sediment was insufficient to maintain the initial concentration in the porewater before consumption. The MeHg fluxes in WL (6.18 ng m^?2 day^?1) were twice those in DL (2.89 ng m^?2 day^?1), and the risk assessment code revealed a higher risk in the surface layer (25.21–61.88%) than in the deep layer (0–27.75%).

Conclusions

Dissolved Hg and MeHg accumulated on the surface of the sediments and were more active than in the deeper sediments. The DGT-labile state can be used for a better understanding of the bioavailability and mobility of Hg. The diffusion direction of Hg and MeHg was from sediment to the overlying water. The release risks of Hg and MeHg from surface sediments (especially in WL) were found to be worthy of concern.

     

Quantitative and qualitative characterisation of humic products with spectral parameters

Purpose

The application of different humic products for the treatment of soils and plants has increased in recent years. The characteristics of humic products, such as the content and composition of organic carbon and the maturity, provide valuable information which is essential for an adequate application. Such information is crucial for manufacturers, business consultants and users involved in the production, distribution and implementation of humic products. This article presents the correlation between the quantitative indicators of commercial humic products and their spectral characteristics via measurements in the ultraviolet spectrum at 300 nm, in the visible area at 445 and 665 nm and in the near-infrared spectrum at 850 nm.

Materials and methods

We evaluated humic products (liquid and solid) of different origins. Via wet combustion, the content of total organic carbon in humic products can be determined. The precipitation of humic acids from the starting solution determines the composition of the humic products in terms of humic acids (HAs) and fulvic acids (FAs). The dissolution of HAs determines their concentration by titration, while the specific extinction can be assessed via spectrophotometry via measuring the absorption of HAs spectra at the following wavelengths: 300, 465, 665 and 850 nm. The degree of aromaticity and condensation of humic products determines the optical density of the HAs via the E₄/E₆ ratio.

Results and discussion

The content of total organic carbon varied widely from 0.55 to 37.5% across all groups. The content of carbon in HAs, as a percentage of the total carbon in fulvic-type humic products, ranged from 1.29 to 16.00%, while in humic-type products, it ranged from 51.43 to 91.92%. The minimum value of the E₄/E₆ ratio was 2.97, while the maximum value was 6.35. We observed a direct relationship between the dominant type of acids in humic products and the E₄/E₆ ratio.

Conclusions

The optical density of HAs indicates their quality characteristics. The presented optical characteristics for humic products show that there is a direct relationship, especially between HAs/FAs and E₄/E₆ ratios. Measurement at 300 nm (E₃₀₀) in the near-ultraviolet area and at 850 nm (E₈₅₀) in the near-infrared area can increase the range of the spectral study.

     

Characterization of stable humic–enzyme complexes of different soil ecosystems through analytical isoelectric focussing technique (IEF)

Conventional parameters (total organic carbon, total nitrogen, humic acids and fulvic acids) frequently associated with soil quality were measured and compared with the amount and activity of β-glucosidases associated with the humic–enzyme complex. Soil quality may be defined as the maintenance of an “enzymatically active humic carbon pool” which may express soil resilience and ecological functions. The combination of ultrafiltration (UF) and isoelectric focussing (IEF) permitted the extraction and purification of the humic-bound β-glucosidases. Even though humic-β-glucosidases represent only a small part of soil humic matter either in terms of total soil β-glucosidase activity (3–21%) or as a proportion of the humic-C content (4–8%), they proved to be discriminating parameters (significative differences at P < 0.05) for defining soil biochemical quality. Specifically, on the basis of the amount of β-glucosidase activity in the humic fraction >10⁴ Da (IEF peaks in the pH range 3.5–4.5), the soils were distributed in a decreasing order of quality: undisturbed meadow > tree plantation > 60-year vineyard > agricultural soil > 1-year vineyard.     

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.