Composition and reactivity of DOC in forest floor soil solutions in relation to tree species and soil type

Metal coordinating propertiesof DOC (dissolved organic carbon), and henceits influence on heavy metal release andmineral weathering, depend on the compositionand properties of DOC. Tree species producelitter with different chemical composition anddegradability, and these differences mightinfluence the composition and reactivity of DOCin soil solutions. Accordingly, analysis ofcomposition and reactivity of DOC in soilsolution samples collected by centrifugationfrom 16 forest soil O horizons from the fourtree species beech (Fagus sylvatica L.),oak (Quercus robur L.), grand fir (Abies grandis Lindl.), and Norway spruce (Picea abies (L.) Karst.) on two clayey and twosandy soils were carried out. The compositionand properties of DOC were determined bycapillary zone electrophoresis, acid-basetitration, Cu ion titration, total elementalanalysis, IR and UV spectroscopy, and metalrelease assays. Concentrations of DOC rangedfrom 20 to 163 mM with pH ranging from 4.6 to7.3. Norway spruce produced the highest DOCconcentration, and the lowest pH. Carbon inlow-molecular-weight aliphatic carboxylic acids(LACA) accounted for less than 6% of DOC withformic and acetic acids as the most abundantLACAs. The DOC was cation exchanged and protonsaturated to obtain comparable forms of DOC.Titratable carboxylic acid and phenolic groupswere in the range 51 to 82 and 20 to64 mmol·mol^–1 C, respectively, with fewerphenolic groups in grand fir DOC as the onlysignificant difference. Infrared spectra offreeze-dried DOC samples suggest low contentsof aromatic C in the DOC especially from grandfir stands. Stability constants, log K of Cu-DOC complexes, determined by Cu ion titrationof DOC samples with fitting of the data to atwo-site binding model, were in the range 5.63to 6.21 for the strong binding sites and 3.58to 4.10 for the weak sites, but with nosignificant effects of tree species or site.Freeze-dried DOC samples were found to consistof 41 to 45% C, 38 to 49% O, 4.4 to 5.4% Hand 1.2 to 2.0% N and C/N ratios in the range26 to 42. Reactivity of DOC in terms of releaserates of Cd, Cu and Fe cations from a soilsample (flow cell experiments) showed nosignificant differences among DOC samples fromdifferent tree species and soil types.Apparently, only minor differences occur inchemical composition and reactivity ofequivalent concentrations of DOC in forestfloor soil solutions irrespective of origin,i.e. four tree species and two soil types. Soilsolution pH and the concentration of DOCproduced by various tree species are thecritical parameters when distinguishing amongtree species in relation to heavy metal releaseand mineral weathering.     

Low-molecular-weight aliphatic carboxylic acids in soil solutions under different vegetations determined by capillary zone electrophoresis

Concentrations of low-molecular-weight aliphatic carboxylic acids in soil solution were determined by a newly developed capillary zone electrophoresis method. Soil solution samples were collected by centrifugation of soil from the A horizon of a Danish, homogeneous, nutrient-rich Hapludalf in adjacent forested and arable plots. The forested plots of 0.5 ha were 33-year old stands of beech (Fagus sylvatica L.), oak (Quercus robur L.), grand fir (Abies grandis Lindl.), and Norway spruce (Picea abies (L.) Karst.), while sugar beet (Beta vulgaris L.) and winter wheat (Triticum aestivum L.) were the agricultural crops this year. High variability in soil solution concentrations of metal cations (Al, Ca, K, Mg, Na), monocarboxylic acids (formic, acetic, lactic, and valeric acids), and di- and tricarboxylic acids (oxalic, malic, succinic, and citric acids) were found within each plot. Despite this short-range within-plot variability, higher concentrations of di- and tricarboxylic acids were found in the forested soils than in the arable soils. The vegetation seemed to favour some monocarboxylic acids, but the total monocarboxylic acid concentrations showed little relation to the vegetation. Probably due to much less soil water in the Norway spruce plot, the low-molecular-weight aliphatic carboxylic acid concentrations in the samples from that plot were much higher than those found in samples from the other plots. Carbon in low-molecular-weight aliphatic carboxylic acids only accounts for a few percent of dissolved organic carbon, and no general relation was found between carbon in low-molecular-weight aliphatic carboxylic acids and dissolved organic carbon, although the correlation between carbon in di- and tricarboxylic acids and dissolved organic carbon was significant. This revised version was published online in June 2006 with corrections to the Cover Date.     

Effect of endophytic fungi on cadmium tolerance and bioaccumulation by Festuca arundinacea and Festuca pratensis

Endophytic fungi are a group of fungi that live asymptomatically inside plant tissue. These fungi may increase host plant tolerance to biotic and abiotic stresses. The effect of Neotyphodium endophytes in two grass species (Festuca arundinacea and Festuca pratensis) on cadmium (Cd) tolerance, accumulation and translocation has been our main objective. The plants were grown in a hydroponic system under different Cd concentrations (0, 5, 10, and 20 mg L(-1)) for 6 weeks. They were also grown in soil spiked with different concentrations of Cd (0, 10, 20, and 40 mg kg(-1)) for 2 months. The results from all Cd treatments showed higher biomass production (12-24%) and higher potential to accumulate Cd in roots (6-16%) and shoots (6-20%) of endophyte-infected plants than endophyte-free plants. Cadmium accumulation by plants indicated that the grasses were capable of Cd hyperaccumulation, a property that was augmented after endophyte infection. Maximum photochemical efficiency of photosystem II (Fv/Fm) revealed that Cd stress was significantly reduced in endophyte-infected plants compared to non-infected ones.     

pH buffering in acidic soils developed under Picea abies and Quercus robur – effects of soil organic matter, adsorbed cations and soil solution ionic strength

Soil solution chemistry, soil acidity andcomposition of adsorbed cations were determinedin two soil profiles developed under a mixedspruce (Picea abies and Piceasitchensis) stand and in one soil profiledeveloped under an oak (Quercus robur)stand. Soils under spruce were classified asSpodosols and soils under oak were classifiedas Inceptisols. All profiles were developed inthe same parent material; a Saahlian sandy tillcontaining less than 2% clay. In the mineralsoil, the contribution from mineral surfaces tothe total cation-exchange capacity (CEC_t)was estimated to be less than 3%. Soilsolution pH and the percent base saturation ofCEC_t [%BS = 100 (2Ca + 2Mg + Na + K)CEC_t ^–1] were substantially lower inthe upper 35–40 cm of the two Spodosols, ascompared to the Inceptisol. The total amount ofsoil adsorbed base cations (BC) did not differamong the three profiles on an area basis downto 1 m soil depth. Thus, soil acidification ofCEC_t due to net losses of BC could notexplain differences in soil pH and %BS amongthe soil profiles. A weak acid analogue, takingthe pH-effect of metal complexation intoconsideration, combined with soil solutionionic strength as a covariate, could describeboth the pH variation by depth within soilprofiles and pH differences between theInceptisol and the two Spodosol profiles. Ourresults confirm and extend earlier findingsfrom O and E horizons of Spodosols that theextent to which organic acid groups react withAl minerals to form Al-SOM complexes is a majorpH-buffering process in acidic forest soils. Wesuggest that an increasing Al-saturation of SOMis the major reason for the widely observed pHincrease by depth in acidic forest soils with apH less than approximately 4.5. Our resultsstrongly imply that changes in mass of SOM, theionic strength in soil solution and therelative composition of soil adsorbed Al and Hneed to be considered when the causality behindchanges in pH and base saturation isinvestigated.     

Addressing speciation in the effect factor for characterisation of freshwater ecotoxicity—the case of copper

Purpose  

Determination of the ecotoxicity effect factor (EF) in life cycle impact assessment (LCIA) is based on test data reporting the total dissolved concentration of a substance. In spite of the recognised influence of chemical speciation and physico-chemical characteristics of the aquatic systems on toxicity of dissolved metals, these properties are not considered when calculating characterization factors (CFs) for metals. It is hypothesised that the main cause of the variation in reported EC50 values of Cu among published test results lies in different speciation patterns for Cu in the test media, and that the toxicity of Cu is predominantly caused by the free Cu²⁺ ion. Hence, the free Cu²⁺ ion concentration should substitute the total dissolved metal concentration when determining the EF.     

A Laboratory Assessment of Potentials and Limitations of Using EDTA,Rhamnolipids, and Compost-derived Humic Substances (HS) in Enhanced Phytoextraction of Copper and Zinc Polluted Calcareous Soils

Phytoextraction is an economically and environmentally attractive in-situ method for cleaning heavy metal polluted soil. Phytoextraction is a rather slow process, but it can be enhanced by the application of chelating agents such as the synthetic ethylenediaminetetraacetic acid (EDTA). However, EDTA is persistent, toxic, and can promote heavy metal leaching. Replacement of EDTA by natural, non-toxic compounds such as humic substances (HS) or rhamnolipids (bacterial-produced biosurfactants) might be environmentally attractive but before recommending such alternatives, their suitability must be assessed. Therefore, compost-derived HS and rhamnolipids were compared with EDTA as natural non-toxic alternatives in a multi-step batch extraction test. The test included 10 steps carried out on two Cu and Zn polluted calcareous soils using a solution:soil ratio of 10 (L/kg). In each step, soil was extracted with an extractant containing EDTA, HS, or rhamnolipids corresponding to 250 mmol DOC/kg of soil (3 g C/kg). By HS extraction, each step resulted in the release of ～0.29 mg Cu/L and ～0.19 mg Zn/L, which is considered to enhance plant uptake without leading to unacceptable leaching and toxification of the plants (and the environment), suggesting HS can enhance phytoextraction. In contrast, the EDTA and the rhamnolipid treatments were found to be unsuitable because the EDTA released Cu and Zn in concentrations that may be toxic to plants and can lead to leaching, whereas the rhamnolipids showed insufficient capacity to mobilize Cu (and Zn). However, future investigations in the field are needed to confirm these laboratory results.     

Mycorrhiza and root hairs in barley enhance acquisition of phosphorus and uranium from phosphate rock but mycorrhiza decreases root to shoot uranium transfer

Some phosphate rocks (PR) contain high concentrations of uranium (U), which are potentially toxic via accumulation in soils and food chains, and plant uptake of U is likely to be influenced by characteristics of roots and associated microorganisms. The relative importance of root hairs and mycorrhiza in U uptake from PR was studied using a root hairless barley (Hordeum vulgare) mutant (Brb) and its wild type (WT). Both plant genotypes were grown in pots with Glomus intraradices BEG 87, or in the absence of mycorrhiza, and three P treatments were included: nil P, 2% (w/w) PR and 50 mg KH(2)PO(4)-P kg(-1) soil. Mycorrhiza markedly increased d. wts and P contents of Brb amended with nil P or PR, but generally depressed d. wts of WT plants, irrespective of P amendments. Mycorrhiza had contrasting effects on U contents in roots and shoots, in particular in Brb where mycorrhiza increased root U concentrations but decreased U translocation from roots to shoots. The experiment supports our understanding of arbuscular mycorrhiza as being multifunctional by not only improving the utilization of PR by the host plant but also by contributing to the phytostabilization of uranium.     

Experimental Assessment of Using Soluble Humic Substances for Remediation of Heavy Metal Polluted Soils

Since heavy metals are nondegradable and strongly bonded in soils, remediation of heavy metal polluted soils by extraction is difficult and current extraction techniques require harsh chemicals such as ethylenediaminetetraacetic acid (EDTA). However, use of EDTA is environmentally problematic because of costs, persistence, toxicity and deterioration of soil structure. Therefore, the potential of soluble natural humic substances (HS) to extract heavy metals from contaminated soils is tested as an environmentally friendly substitute for EDTA. A strongly polluted, calcareous urban soil (CRC soil) and a moderately polluted agricultural soil (CUP soil) were extracted at neutral pH in batch mode by three HS solutions from beech and Norway spruce litter (Beech-HS and Spruce-HS) and processed cow slurry (Bio-HS), all containing 25 mM dissolved organic carbon (DOC). After 10 extractions with a solution to soil ratio of 5:1 (L/kg), 8% to 39% of the total Cd, Cu, Ni and Pb soil contents, lowest for Ni and highest for Cu/Pb, were extracted. Natural and processed HS samples had comparable capacities to extract the heavy metals. A comparison of 100 mM DOC of Bio-HS and EDTA as extractants for Cu from the CRC soil showed extraction of 67% by EDTA and 41% by Bio-HS, indicating somewhat higher efficiency of EDTA than of HS. Sequential extraction of the CRC soil after Bio-HS and EDTA extraction showed removal of exchangeable, carbonate- and metal oxide-bound Cu but also of some residual Cu. It is therefore concluded that HS appears to be an attractive and promising alternative to EDTA as remediation agent for heavy metal polluted soils provided cheap HS of good quality is easily available.