Limitations for revegetation in lead/zinc minesoils (NW Spain)

Purpose

Metal mining is the main cause of soil contamination caused by heavy metals. Mine tailings and minespoils generally offer hostile environments for plant growth due to their low nutrient availability, low organic matter content, and high trace metal content. This study was carried out with the aim of characterizing the soils that have developed on the tailings from an abandoned lead and zinc mine in Galicia (NW Spain) and determining the soil factors that limit revegetation.

Materials and methods

We selected three zones: (a) the minespoils, (b) in the mining area, and (c) the settling pond, where the sludge from the flotation process was deposited. A control soil was also sampled outside of the mining area. We analyzed the physicochemical properties and metal levels in the mine spoil and soil samples we collected.

Results and discussion

The results indicate that the main physical limitations of minesoils are their low effective depth, high porosity and stoniness, while the main chemical limitations are low organic matter content and low CEC and an imbalance between exchangeable cations. These minesoils are strongly affected by high Zn and Pb levels which hinder revegetation.

Conclusions

As high concentrations of toxic trace elements and a high pH are important factors in limiting the plant growth, the restoration procedure must overcome the oxidation processes by adding organic amendments that also contribute towards fixing heavy metals or by implanting spontaneous vegetation adapted to the mine conditions, such as common broom (Cytisus scoparius) or white birch (Betula celtiberica).     

Thermodynamic parameters of enzymes in grassland soils from Galicia, NW Spain

The thermodynamic parameters of the enzymes catalase, dehydrogenase, casein-protease, α-N-benzoyl-l-argininamide (BAA)-protease, urease, Carboxymethyl (CM)-cellulase, invertase, β-glucosidase and arylsulphatase, were investigated in grassland soils from a European temperate-humid zone (Galicia, NW Spain). The effect of temperature on enzyme activity was determined at 5, 18, 27, 37, 57 and 70 °C. The temperature-dependence of the rate of substrate hydrolysis varied depending on the enzyme and soil. In general, the soil containing the least amount of organic matter (OM) showed the lowest enzyme activity for all temperatures and enzymes, whereas soils with similar OM contents showed similar levels of activity for the entire temperature range. Temperature had a noteworthy effect on the activity of oxidoreductases. Product formation in the reaction catalyzed by dehydrogenase increased with increasing temperature until 70 °C, which was attributed to chemical reduction of iodonitrotetrazolium violet (INT) at high temperatures. Catalase activity was not affected above 37 °C, which may be explained either by non-enzymatic decomposition of hydrogen peroxide or by the fact that catalase has reached kinetic perfection, and is therefore not saturated with substrate.The Arrhenius equation was used to determine the activation energy (E_a) and the temperature coefficient (Q₁₀) for all enzymes. The values of E_a and Q₁₀ for each enzyme differed among soils, although in general the differences were small, especially for those enzymes that act on substrates of low molecular weight. In terms of the values of E_a and Q₁₀ and the differences established among soils, the results obtained for those enzymes that act on substrates of high molecular weight differed most from those corresponding to the other enzymes. Thus the lowest E_a and Q₁₀ values corresponded to BAA-protease, and the highest values to CM-cellulase and casein-protease. Except for catalase in one of the soils, the values of E_a and Q₁₀ for the oxidoreductases were similar to those of most of the hydrolases. In general, the effect of temperature appeared to be more dependent on the type of enzyme than on the characteristics of the soil.     

Mobility of sulphate in experimentally acidified soils from Galicia (NW Spain)

Retention of S0₄ ^2? was investigated in Galician soils throughout an intense regime of acidification. Experiments consisted of the addition of an H2SO4 solution (pH 2.7) to columns of 6 soils of contrasting properties over 1, 2, or 5 months. Leachates were obtained continuously throughout the experiment for analysis, and analysis made of the solid fractions after 1, 2 or 5 months. The greatest capacities for retention of S0₄ ^2? were found in soil developed from serpentine and micaschist; the lowest in soils from granite, slate and sandy sediments. The surface horizons, especially those rich in organic matter, displayed low retention of 5042-. The amount of S0₄ ^2? adsorbed throughout the experiment depended on the content of crystalline forms of Fe and with the Fe and Al extracted with dithionite-citrate.The low retention of S0₄ ^2? in the organic horizons and the slightly negative relation with the organic matter suggest an inhibitory effect of the organic matter on the S0₄ ^2? retention process. Results of the study show, that under conditions of moderate acidity, SO₄ ^2? retention occurs in the form of adsorption; in strongly acidic conditions, the precipitation of aluminium-sulphate minerals may provide an additional retention mechanism.     

Copper distribution and acid-base mobilization in vineyard soils and sediments from Galicia (NW Spain)

In northern Spain and elsewhere in the world, many vineyards are located on steep slopes and are susceptible to accelerated soil erosion. Contaminants, notably Cu, originating from repeated application of copper‐based fungicides to the vines to prevent mildew, are transported and stored in the sediments deposited close to valley bottoms. In this study, the contents and distribution of Cu in 17 soil samples and 21 sediment samples collected from vineyard stands were determined. In addition, the effect of pH on Cu release from vineyard soils and sediments was quantified. The total Cu content (Cu_T) in the soils varied between 96 and 583 mg kg^?1, and was between 1.2 and 5.6 times greater in sediment samples. The mean concentration of potentially bioavailable Cu (Cu_EDTA) in the sediments was 199 mg kg^?1 (46% of Cu_T), and was 80 mg kg^?1 (36% of Cu_T) in the soils. Copper bound to soil organic matter (Cu_OM) was the dominant fraction in the soils (on average, 53% of the Cu_T), while in sediment samples Cu_OM values varied between 37 and 712 mg kg^?1 and were significantly greater (P < 0.01) than in the soils. Copper associated with non‐crystalline inorganic components (Cu_IA) was the second most important fraction in the sediments, in which it was 3.4 times greater than in the soils. Release of Cu due to changes in the pH followed a U‐shaped pattern in soils and sediments. The release of Cu increased when the pH decreased below 5.5 due to the increased solubility of the metal at this pH. When the pH increased above 7.5, Cu and organic matter were released simultaneously.     

Expression of andic properties in soils from Galicia (NW Spain) under forest and agricultural use

The organic matter (OM) of soils with andic properties has long been considered highly stable because of the presence of Al–humus complexes and sorption of organic ligands onto amorphous compounds. In this study, we characterized soils under different land use regimes located within an amphibolitic massif close to Santiago de Compostela (Spain), where soils with andic properties are present. Slash and burn agriculture was a common practice in the area until the second half of the 20th century. Thereafter, modern agriculture was progressively introduced into the area (AGR soils), and the rest of the land was either reforested or abandoned (FOR soils). We found that the mean organic C content of AGR soils (48.7 g kg^?1) was ～ 50% that of FOR soils (94.2 g kg^?1). Mean soil pH was significantly greater (P < 0.05) in the AGR than in the FOR soils (4.95 compared with 4.63), which is attributed to liming and Ca‐phosphate fertilization of the former. Mean concentrations of the Al forms studied (extractable with CuCl₂, sodium pyrophosphate, ammonium oxalate, or NaOH) were significantly smaller (P < 0.01) in AGR (1.4, 4.9, 9.3, 11.0 g kg^?1, respectively) than in FOR soils (3.9, 10.2, 16.5, 17.9 g kg^?1, respectively). The results show the vulnerability of the OM and Al–humus complexes in these soils to modern agricultural practices, which has led to the attenuation – and in some cases even the disappearance – of andic soil properties in a relatively short time (< 30 years) following changes in land use/management. We propose the inclusion of the formative element ‘andic’ in the criteria for the definition of Umbrisol subunits; this would avoid the abrupt discontinuity observed in the current World Reference Base classification.     

Effect of management and climate on biochemical properties of grassland soils from Galicia (NW Spain)

Biochemical properties are considered to be the best indicators available at present for assessing soil quality. However, there are still many gaps in our knowledge about how these properties are affected by abiotic factors and how these factors interact with soil management. With the aim of understanding how climate and soil management affect soil biochemical properties in grasslands soils from a temperate-humid area (Galicia, NW Spain), a total of 60 soils were analyzed for several microbial and biochemical properties. Grasslands were divided into groups according to the type of management applied (native compared with intensive) and to the climate in the area where they were sampled (Mediterranean subhumid with centroeuropean drift climate compared with Atlantic climate). We found that management had a greater influence on soil biochemical properties than climate. Altitude, which strongly influences climate in the region where the soils were analyzed, was found to be a significant factor that affected most soil biochemical properties. In conclusion, the results show that microbially-mediated processes are greatly affected by both, management and abiotic factors and that, for some properties (like net N mineralization and cellulase and casein-protease activities), abiotic factors can have an important influence on soil biochemical properties.     

Response of some soils of Galicia (NW Spain) to H2SO4 acidification

This paper presents the results of an acidification experiment, consisting of seven consecutive equilibrations of repesentative soils of Galicia with a H₂SO₄ solution (pH 3). Different responses to soil acidification, such as SO₄ retention and cation release, were evaluated. In soils derived from gabbro and amphibolite, SO₄ retention and Al release were the principal acid neutralization mechanisms, whereas in soils derived from granite, schist, shale and sandstone Al release was the main process. The SO₄ retention was significantly correlated with Al and Fe extracted with dihionite-citrate-bicarbonate and crystalline Fe. The released base cations came mainly from exchange sites, though sometimes also from other sources, probably by mineral weathering. The major sources of Al in these soils were metalorganic complexes and weatherable minerals. Solutions with pHs close to 4 are in equilibrium with gibbsite, kaolinite, jurbanite and alunite; at lower pH values, with jurbanite and alunite.     

Comparison of indirect methods for the determination of percent exchangeable aluminium in acid soils of Galicia (NW Spain)

Abstract

Ten easily determined soil parameters related to soil acidity were evaluated for their potential to provide simple, indirect estimates of the exchangeable aluminium percentage (PAL). These parameters were correlated with the PAL in 0.6N BaCl₂ extracts of soils collected from lime trials on 4 different parent materials. Six rates of lime (0, 0.75, 1.5, 3, 6, 12 t/ha) were added 3–4 years prior to collection of the samples. The soil parameters examined were the pH of soil suspensions with SMP, Woodruff and New Woodruff buffer solutions; the pH of 1, 5 and 10mM CaCl₂ and 0.6N BaCl₂ soil extracts, and the aluminium content of 1, 5 and 10mM CaCl₂ soil extracts. The best correlations with the exchangeable aluminium percentage for all soils considered, were those based on the aluminium content of the 5mM CaCl₂ extract (r=0.976, n=24) followed by the pH of the 0.6N BaCl₂ extract (r=0.945, n= 24). Both these methods are suggested as reliable indirect estimates of soil exchangeable alumimium percentage where availability of staff or equipment restrict direct determinations.     

Wildfires influence on soil organic matter in an Atlantic mountainous region (NW of Spain)

The principal aim of this research was to determine the influence of wildfires on soil organic matter (SOM) content and composition in soils located on the northern slope of the Cantabrian Cordillera, an Atlantic mountainous region in the North West of Spain, where wildfires are frequent. Samples from soils with similar aspect, slope, elevation and vegetation characteristics, but with different wildfires histories were collected. Total organic carbon and total nitrogen contents were determined as well as the C/N ratio. Furthermore, a qualitative characterization of the soil organic carbon (SOC) was carried out by ¹³C variable amplitude cross polarization magic angle spinning (VACP/MAS) Nuclear Magnetic Resonance (NMR) spectroscopy. Our results show that, on the one hand, all the sampled soils can be considered important pools of carbon in this Atlantic mountainous region, especially in the heath areas. On the other hand, the fire-affected soils present higher SOM contents than their unburnt counterparts. This could be attributed to an important reaccumulation of fresh vegetal material, which is probably a consequence of the decrease of SOM decomposition rates after fire. Moreover, charred organic compounds are not found in all the burnt soils, which could be due to the long time since the last fires events took place, to different fire severities, or to different post-fire erosion processes in the studied soils.     

Micromorphological evidence of black carbon in colluvial soils from NW Spain

Biomass burning produces a residue called black carbon (BC). Black C is generally considered to be highly resistant against biodegradation and has a potential role in the global C cycle, but is difficult to identify and quantify when subjected to prolonged degradation in terrestrial sediments. The colluvial soils from Campo Lameiro (NW Spain), also known as ‘Atlantic rankers’, are rich in organic matter (up to 140 g C kg^?1 soil). A micromorphological study was undertaken to test the hypothesis that a large proportion of the organic matter was derived from BC formed during Holocene wildfires (up to > 6000 years ago). As roughly estimated from image analysis of 12 thin sections, the volumetric BC contribution ranged between 10 and 60% (26% on average) of the organic matter. This is a conservative estimate as additional morphologically unrecognizable BC was present in the microgranular matrix of coalesced excrement. We conclude that (i) currently unknown quantities of BC are stored in Atlantic rankers and (ii) analysis of thin sections is an effective tool to identify BC.     

Correlations between soil parameters and radionuclide contents in samples from Biscay (Spain)

The distribution of gamma emitting radioactive constituents in Biscay soils have been measured in 15 cm cores, at three depth levels, in fourteen sampling positions. Analyses were performed in Marinelli beakers with a gamma multichannel analyser provided with a Ge-HP detector. Additionally, each soil was characterized by a number of parameters (position, bulk density, pH, size distribution, total contents of carbon, nitrogen and hydrogen, thermogravimetric data and major cations soluble in ammonium acetate at pH 7). Seven natural radioisotopes (⁴⁰K, ²²⁸Ac, ²¹²Bi, ²⁰⁸TI, ²²⁶Ra, ²¹⁴Pb and ²¹⁴Bi) and ¹³⁷Cs were detected and measured. Relations between natural radionuclides (located before and after radon isotopes in both radioactive series) and soil parameters are mainly explained by two statistical multivariate methods (factor analysis and numerical taxonomy). The more complex dependence of radiocaesium contents on soil characteristics was elucidated by linear multiple regression.     

Plant heavy metal concentrations and soil biological properties in agricultural serpentine soils

Abstract

Soils developed on serpentinitic rocks have serious limitations for agriculture. They have high levels of magnesium (Mg) and heavy metals [copper (Cu), manganese (Mn), nickel (Ni), and chromium (Cr)] and are deficient in some macronutrients. In parts of Northwestern Spain, serpentine soils have been subjected to intensive management, based on the use of manure and harvesting residues. Although these practices have allowed the growth of crops, plants may have accumulated high amounts of metals. This study was carried out to assess the effect of the management practices on the uptake of heavy metals by crops, and to analyze the relationship between the concentrations of these metals in plants, and soil properties. Moderate levels of Ni and Mn and low levels of Cr and Cu were found in soil extractable fractions of these metals. In spite of this, analysis of plant tissues revealed high levels of Cr and Ni and moderate contents of Mn. Concentrations of Mn and Ni in foliage were correlated to soil extractable contents, whereas simple linear regression between concentration of Cr in plants and the soil‐extractable Cr showed a poor relationship, possibly because the availability of this metal, as Cr(VI), is determined by temporal environmental conditions. To assess the effects of the management on the uptake of heavy metals by plants, a complementary bioassay experiment was carried out in the laboratory in which Festuca rubra and Agrostis stolonifera were sown on serpentine soil with low organic matter content, and amended with peat and/or lime. This experiment confirmed that there is a reduction in heavy metal concentration in plants after organic amendment and suggested that the lower metal availability is partly due to the higher soil microbial activity, produced as a consequence of addition of organic matter.     

Throughfall,runoff and soil erosion after prescribed burning in gorse shrubland in Galicia (NW Spain)

The first‐year effect of two different prescribed burning treatments on throughfall, runoff and soil erosion was evaluated in gorse shrubland (Ulex europaeus L.) in Galicia (NW Spain). The treatments compared were: intense burn, light burn and control (no burn). Accumulated annual throughfall represented between the 81 and 87 per cent of total rainfall in intensely burned and lightly burned areas, respectively, whereas in the unburnt areas it was 60 per cent. No significant differences between burning treatments were found for the annual throughfall. However, runoff was significantly greater in intensely burned plots (1·5‐times) than in lightly burned plots. Burning also resulted in a significant increase in runoff (between 2·5 and 1·7‐times, respectively) compared with controls. Total soil losses were small in all treatments, but the intense burn caused significantly greater soil erosion (5·8‐times) compared with the unburned areas. Soil losses after the light burn did not significantly differ from the control although they were higher (2·3‐times). The relationships obtained between erosion and several rainfall parameters were significantly different in burned areas compared to the control. The same response was observed for runoff. Annual erosion losses showed a strong dependence on percentage of bare soil even for small values of this variable. Litter thickness was also a very important variable influencing on erosion rates. This study indicated that by combining ignition techniques and high litter moisture content to maintain the percentage of bare soil below 85 per cent, soil erosion was low. Nevertheless, this result was constrained by the low rainfall that occurred during the study. Copyright © 2005 John Wiley & Sons, Ltd.     

Pedological and geomorphological cycles in a catena of Galicia (NW Spain)

A catena developed on gabbro in Galicia, N.W. Spain, was studied. The methods utilized, consisting of macro- and microscopic mineralogical and morphological observation, allowed the identification of different features produced by the action of pedological and geomorphological processes. The application of Butler's K cycle concept allows a relative sequence of events to be established in which pedogenetic processes are integrated within the general framework of the evolutionary history of the slope. Five K cycles could be recognized, beginning with a phase of deep weathering and ending with the present phase of incipient soil formation. In between feature a.o. phases of solifluxion, the formation of an argillic horizon and the development of a stoneline.     

Chemical and mineralogical changes in a polygenetic soil of Galicia,NW Spain

The soils of Galicia, NW Spain, developed on gabbro often include one or more buried profiles. In the modern overlying soil, gibbsite is common and the Fe oxyhydroxides include maghemite. In the buried soil interstratified kaolinite–smectite is abundant, gibbsite is present in traces and the Fe oxyhydroxides are mostly formed by goethite. Chemical and mineralogical data show that the modern soil has developed under strongly leaching conditions that contrast with those in which the buried soil formed. We suggest that the interstratified kaolinite–smectite is a relict mineral that helps reconstruction of the pedogenetic history of these soils.     

Solid-Solution Metal Partitioning for the Upper Mero River Basin (NW Spain)

This study determines the seasonal variability of metal partition coefficients [aluminium (Al), iron (Fe), manganese (Mn), copper (Cu), and zinc (Zn)] and analyses the importance of suspended sediments (SS), dissolved organic carbon (DOC) concentrations, pH, and discharge (Q) on the seasonal variability of metal partition coefficients (K_Ds) in the headwaters of the Mero River catchment, which drains an agroforestry area in northwestern Spain. Metal partition coefficients were used as an approach to relate dissolved and particulate fractions. Water samples were collected over 3 years (2005–2008) at the catchment outlet. The mean metal dissolved concentrations were: Fe (43.5 μg L^?1) > Al (23.3 μg L^?1) > Zn (1.8 μg L^?1) > Mn (1.2 μg L^?1) > Cu (0.3 μg L^?1). Partition coefficients followed the order Mn > Al > Fe > Zn > Cu, and their values exhibited low variability. Al, Cu, and Zn partition coefficients presented the greatest values in summer, except during 2007–2008, when the greatest K_Ds value was observed in autumn, whereas the K_Ds of Fe showed the greatest values in winter. The K_D of Mn has no seasonality. For Al, Cu, and Zn, the seasonal SS concentrations were closely related to Kd. For Fe, Kd was more closely related to DOC concentration than to SS concentration.     

Chemical analysis of Teucrium species (Lamiaceae) growing on serpentine soils in Bulgaria

Trace elemental concentrations (Fe, Ni, Mn, Cr, Co, Cu, Zn, Pb, Cd, and As) in aerial biomass (stems, leaves, and flowers) of the medicinal plants Teucrium chamaedrys, T. montanum, and T. polium growing on serpentine soils in Bulgaria were examined in relation to the total element contents in their respective rhizospheric soils. The objectives of the study were to evaluate: (1) elemental concentrations in plant tissues and associated soil samples together with the plants ability to tolerate/accumulate metal concentrations; (2) correlations between total metal concentrations in plants and their rhizospheric soils. Metal concentrations varied across species and sites. Their levels in plant tissues from nonserpentine sites were always lower compared to those from serpentine ones. The highest concentrations for Fe, Ni, Mn, Cr, As, Cu, and Pb were found in T. polium. Positive correlation coefficients were established between Ni, Cr, Fe, Co, and Cu in plants and Ca in the soil. None of the species tested hyperaccumulated metals although the metal concentration in some of them exceeded the range naturally found in plants. The Teucrium species can be considered as “excluders”, containing relatively low metal concentrations in their aerial parts (stems, leaves, and flowers) even in cases of high elemental concentrations in the rhizospheric soil. In all three medicinal plants, metal concentrations for toxic elements were above the permissible limits for pharmaceutical purposes. Therefore, plants found on serpentine bedrock are not recommended to be collected for pharmaceutical purposes.     

Aluminium geochemistry in the bulk and rhizospheric soil of the species colonising an abandoned copper mine in Galicia (NW Spain)

Purpose  

Aluminium partitioning in the solid fraction and aluminium in solution in the bulk and rhizospheric soil of different plant species colonising an abandoned Cu mine slope (Calluna vulgaris, Erica cinerea and Salix atrocinerea) and mine dump (C. vulgaris and E. cinerea) were investigated. The aim of the study was to determine the changes that the species induce in the Al forms in the rhizosphere in order to adapt to heterogeneous substrates.     

Aluminium Toxicity Risk for Pinus pinaster in Acid Soils (Galicia,NW Spain)

The influence of bedrock on aluminium toxicity and aluminium speciation in the soil solution was studied in four Pinus pinaster plots. Growth and biomass parameters in the acidic soils were also evaluated in relation to different Al toxicity indices. The plots were developed over slate, biotitic schist, mica schist and granite. Samples of rhizospheric and non‐rhizospheric soil, 1‐year‐old needles and roots were collected in each study plot. Total Al, reactive Al, acid‐soluble Al, non‐labile and labile Al and Al species (Al³⁺, Al‐OH, Al‐F and Al‐SO₄) were determined in soil solution. Reactive Al dominated over the acid‐soluble Al, and the non‐labile Al predominated over the labile Al in all soils, but particularly over mica schist. In the biotitic schist soil, the Al forms and total Al were lower, whereas concentrations were always higher over mica schist. The Al forms considered most toxic were Al³⁺ and Al‐OH, and Al concentrations were highest over slate and mica schist. Al toxicity indices in soil, needle and roots showed a risk of toxicity in mica schist, slate and granite. The stand site indices over slate and mica schist were lower, consistent with the high labile Al and Al³⁺ + Al‐OH in soil solution. Despite the high stand site index over granite, the growth efficiency was low, in accordance with very low ratios of Ca/Al in needles or fine roots. This confirmed the adaptation of maritime pine to granitic substrates. Copyright © 2016 John Wiley & Sons, Ltd.     

Aluminum speciation in the bulk and rhizospheric soil solution of the species colonizing an abandoned copper mine in Galicia (NW Spain)

Purpose  

The present study was carried out to identify and quantify the aluminum species present in the bulk and rhizospheric soil solution of the spontaneous vegetation colonizing the dump (Calluna vulgaris, Erica cinerea) and slope (C. vulgaris, E. cinerea, Salix atrocinerea) of an abandoned Cu mine in Touro (Galicia, NW Spain).