Efficiency of large-scale aided phytostabilization in a mining pond.

Mining activities accumulate large quantities of waste in tailing ponds, which results in several environmental impacts. In Cartagena-La Unión mining district (SE Spain), a field experiment was carried out in a tailing pond to evaluate the effect of aided phytostabilization on reducing the bioavailability of zinc (Zn), lead (Pb), copper (Cu) and cadmium (Cd) and enhancing soil quality. Nine native plant species were planted, and pig manure and slurry along with marble waste were used as amendments. After 3 years, the vegetation developed heterogeneously on the pond surface. In order to evaluate the factors affecting this inequality, four areas with different VC and an area without treatment (control area) were sampled. Soil physicochemical properties, total, bioavailable and soluble metals, and metal sequential extraction were determined. Results revealed that pH, organic carbon, calcium carbonate equivalent and total nitrogen increased after the aided phytostabilization, while electrical conductivity, total sulfur and bioavailable metals significantly decreased. In addition, results indicated that differences in VC among sampled areas were mainly owing to differences in pH, EC and concentration of soluble metals, which in turn were modified by the effect of non-restored areas on close restored areas after heavy rains due to a lower elevation of the restored areas compared to the unrestored ones. Therefore, to achieve the most favorable and sustainable long-term results of aided phytostabilization, along with plant species and amendments, micro-topography should be also taken into consideration, which causes different soil characteristics and thus different plant growth and survival.

Soil Water Content Prediction Using Electrical Resistivity Tomography (ERT) in Mediterranean Tree Orchard Soils.

Water scarcity in arid and semiarid regions poses problems for agricultural systems, awakening special interest in the development of deficit irrigation strategies to improve water conservation. Toward this purpose, farmers and technicians must monitor soil water and soluble nutrient contents in real time using simple, rapid and economical techniques through time and space. Thus, this study aimed to achieve the following: (i) create a model that predicts water and soluble nutrient contents in soil profiles using electrical resistivity tomography (ERT); and (ii) apply the model to different woody crops under different irrigation regimes (full irrigation and regulated deficit irrigation (RDI)) to assess the efficiency of the model. Simple nonlinear regression analysis was carried out on water content and on different ion contents using electrical resistivity data as the dependent variable. A predictive model for soil water content was calibrated and validated with the datasets based on exponential decay of a three-parameter equation. Nonetheless, no accurate model was achieved to predict any soluble nutrient. Electrical resistivity images were replaced by soil water images after application of the predictive model for all studied crops. They showed that under RDI situations, soil profiles became drier at depth while plant roots seemed to uptake more water, contributing to reductions in soil water content by the creation of desiccation bulbs. Therefore, the use of ERT combined with application of the validated predictive model could be a sustainable strategy to monitor soil water evolution in soil profiles under irrigated fields, facilitating land irrigation management.

Concentration and chemical distribution of metals and arsenic under different typical Mediterranean cropping systems.

Soil under an intensive agriculture production could result in metal pollution if bad management practices are carried out. The aims of this study were to evaluate the influence of cropping systems on soil metal(loid)s accumulation and speciation and to identify metal sources for each cropping system. To achieve these objectives, 40 soil samples from cereal, fruit, citrus and horticultural cropping areas and 15 samples from non-disturbed areas were collected. pH, salinity, particle size distribution, organic carbon and carbonate contents were analysed. In addition, total, DTPA-extractable and water-soluble Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn and As concentrations and their chemical speciation were determined. Results showed an enrichment of Pb in cereal and horticultural soils, of Zn in fruit and horticultural soils and of Cu and Cd in citrus soils. The most available metals were Pb and Cd which was due to their ability to bind to carbonate and reducible phases of soils. The PCA suggested an anthropogenic origin of Pb, Cd, Cu and Zn in most of the cropping systems; this origin was related to both agriculture management practices and other anthropic actions, such as traffic. Therefore, changes in crop managements are necessary for a sustainable agriculture in the studied crop systems.

Phytoremediation Potential of Native Plant Species in Mine Soils Polluted by Metal(loid)s and Rare Earth Elements.

Mining activity has an adverse impact on the surrounding ecosystem, especially via the release of potentially toxic elements (PTEs); therefore, there is an urgent need to develop efficient technologies to remediate these ecosystems, especially soils. Phytoremediation can be potentially used to remediate contaminated areas by potentially toxic elements. However, in soils affected by polymetallic contamination, including metals, metalloids, and rare earth elements (REEs), it is necessary to evaluate the behavior of these toxic elements in the soil-plant system, which will allow the selection of the most appropriate native plants with phytoremediation potential to be used in phytoremediation programs. This study was conducted to evaluate the level of contamination of 29 metal(loid)s and REEs in two natural soils and four native plant species (Salsola oppositifolia, Stipa tenacissima, Piptatherum miliaceum, and Artemisia herba-alba) growing in the vicinity of a Pb-(Ag)-Zn mine and asses their phytoextraction and phytostabilization potential. The results indicated that very high soil contamination was found for Zn, Fe, Al, Pb, Cd, As, Se, and Th, considerable to moderate contamination for Cu, Sb, Cs, Ge Ni, Cr, and Co, and low contamination for Rb, V, Sr, Zr, Sn, Y, Bi and U in the study area, dependent of sampling place. Available fraction of PTEs and REEs in comparison to total concentration showed a wide range from 0% for Sn to more than 10% for Pb, Cd, and Mn. Soil properties such as pH, electrical conductivity, and clay content affect the total, available, and water-soluble concentrations of different PTEs and REEs. The results obtained from plant analysis showed that the concentration of PTEs in shoots could be at a toxicity level (Zn, Pb, and Cr), lower than toxic but more than sufficient or natural concentration accepted in plants (Cd, Ni, and Cu) or at an acceptable level (e.g., V, As, Co, and Mn). Accumulation of PTEs and REEs in plants and the translocation from root to shoot varied between plant species and sampling soils. A. herba-alba is the least efficient plant in the phytoremediation process; P. miliaceum was a good candidate for phytostabilization of Pb, Cd, Cu, V, and As, and S. oppositifolia for phytoextraction of Zn, Cd, Mn, and Mo. All plant species except A. herba-alba could be potential candidates for phytostabilization of REEs, while none of the plant species has the potential to be used in the phytoextraction of REEs.

Bio-Monitoring of Metal(loid)s Pollution in Dry Riverbeds Affected by Mining Activity.

The aim of this study was to evaluate the most abundant native plants that could be used as a bio-monitor of metal(loid) concentration in dry riverbeds affected by mining activities. Three plants species and their respective rhizospheric soils were sampled from the El Beal (Piptatherum miliaceum, 15 samples), La Carrasquilla (Foeniculum vulgare, 10 samples), and Ponce (Dittrichia viscosa, 12 samples) dry riverbeds from the mining district of Cartegena-La Unión (SE Spain). There is scanty bibliography of the capacity of these species to be used as bio-monitors in the dry riverbeds. Plants categorized as a bio-monitor were established according to the bioaccumulation factor (BF), mobility ratio (MR), and linear correlations between metal(loid) concentrations in plants tissues (root or stem)-rhizospheric soils. The rhizospheric soils were highly contaminated for As, Cd, Pb, and Zn (Cf ≥ 6), and moderately contaminated for Mn (1 ≤ Cf < 3). Piptatherum miliaceum presented on Cd similar mean concentrations on rhizospheric soil and root, BF = 1.07, with a strong correlation soil-root (r = 0.61, p = 0.02). Therefore, of the three species with the capacity to grow in the area, Piptatherum miliaceum showed characteristics to be considered as a bio-monitor for Cd, with a BF > 1, and a positive-significant correlation between the rhizospheric soil and roots.

Perennial alley cropping contributes to decrease soil CO2 and N2O emissions and increase soil carbon sequestration in a Mediterranean almond orchard.

The implementation of alley cropping in orchards can be a sustainable strategy to increase farm productivity by crop diversification and contribute to climate change mitigation. In this research, we evaluated the short-term effect of alley cropping with reduced tillage on soil CO2 and N2O emissions and soil total organic carbon (TOC) in an almond orchard under Mediterranean rainfed conditions. We compared an almond monoculture with tillage in all plot surface (MC) with almond crop with reduced tillage and growth of Capparis spinosa (D1) and almond crop with reduced tillage and growth of Thymus hyemalis (D2). For two years, soil CO2 and N2O were measured, with soil sampling at the start and end of the experimental period. Results showed that CO2 emission rates followed the soil temperature pattern, while N2O emissions were not correlated with temperature nor moisture. Soil CO2 emissions were significantly higher in MC (87 mg m-2 h-1), with no significant differences between D1 and D2 (69 mg m-2 h-1). Some peaks in CO2 effluxes were observed after tillage operations during warm days. Soil N2O emission rates were not significantly different among treatments. Cumulative CO2 and CO2 equivalent (CO2e) emissions were significantly highest in MC. When CO2e emissions were expressed on a crop production basis, D2 showed the significantly lowest values (5080 g kg-1) compared to D1 (50,419 g kg-1) and MC (87,836 g kg-1), owing to the high thyme yield, additional to the almond yield. No production was obtained for C. spinosa, since at least two more years are required. TOC did not change with time in MC neither D1, but it significantly increased in D2 from 3.85 g kg-1 in 2019 to 4.62 g kg-1 in 2021. Thus, alley cropping can contribute to increase the agroecosystem productivity and reduce CO2 emissions. However, it is necessary to grow evergreen alley crops such as thyme to obtain short-term increases in soil organic matter. Thus, to estimate increases in TOC with alley cropping, the plantation density and the period required by the crop to cover most of the surface are essential factors at planning the cropping strategy.

Heavy metal concentrations in particle size fractions from street dust of Murcia (Spain) as the basis for risk assessment.

Street dust has been sampled from six different types of land use of the city of Murcia (Spain). The samples were fractionated into eleven particle size fractions (<2, 2-10, 10-20, 20-50, 50-75, 75-106, 106-150, 150-180, 180-425, 425-850 µm and 850-2000 µm) and analyzed for Pb, Cu, Zn and Cd. The concentrations of these four potentially toxic metals were assessed, as well as the effect of particle size on their distribution. A severe enrichment of all metals was observed for all land-uses (industrial, suburban, urban and highways), with the concentration of all metals affected by the type of land-use. Coarse and fine particles in all cases showed concentrations of metals higher than those found in undisturbed areas. However, the results indicated a preferential partitioning of metals in fine particle size fractions in all cases, following a logarithmic distribution. The accumulation in the fine fractions was higher when the metals had an anthropogenic origin. The strong overrepresentation of metals in particles <10 µm indicates that if the finest fractions are removed by a vacuum-assisted dry sweeper or a regenerative-air sweeper the risk of metal dispersion and its consequent risk for humans will be highly reduced. Therefore, we recommend that risk assessment programs include monitoring of metal concentrations in dust where each land-use is separately evaluated. The finest particle fractions should be examined explicitly in order to apply the most efficient measures for reducing the risk of inhalation and ingestion of dust for humans and risk for the environment.

Identification of heavy metal sources by multivariable analysis in a typical Mediterranean city (SE Spain).

Problems associated with heavy metal characterization in the majority of sites are often due to multiple sources of pollution. This work presents the results through the use of advanced statistical techniques to identify sources of soil heavy metals in a typical Mediterranean city. The multivariable analysis performed on seven metals identified four sources controlling their variability. Cr, Mn, and Ni contents were associated to soil parent materials; Cd and Pb contents were related to anthropogenic activities, specifically industrial activities and traffic; Cu content is controlled by long-term application of inorganic fertilizers in agricultural areas. Finally, zinc concentration is associated to commercial and outdoor activities in the area. These results were supported by the fact that metals associated to parent material (Cr, Mn, and Ni) were better correlated with soil lithogenic properties, while anthropogenic metals were correlated with more variable soil constituents.

Investigating the relationship between speciation and oral/lung bioaccessibility of a highly contaminated tailing: contribution in health risk assessment.

Anthropogenic activities such as industrial, mining, or agricultural are the main sources of environmental contamination. One of the most problematic contaminations concerns metals and metalloids from mining activities. This contamination raises the question of the environmental risk induced and the spread of this pollution (geographical and trophic) and the associated health risk. The integrated, multi-analytical approach of this study conducted on the mining district of Cartagena-La Union (Murcia, Spain) as part of the Interreg SUDOE European project "Soil Take Care" aims to (i) precisely define the speciation of contaminants of interest (Zn, Pb, Cd, As), (ii) predict the environmental risk related to storage stability, and (iii) establish the link between the speciation of the bearing phases and the associated health risk. To do this, a representative zone in the Cartagena-La Union mining district close to the populations was chosen. A physic-chemical characterization of the samples was performed (pH, electrical conductivity, CEC, and total metal(loid) concentrations), and the mineralogy was determined using XRD and SEM-EDS. The environmental risk was highlighted from sequential BCR-type extractions and EN-12457 leaching tests. Finally, the health risk was defined using the PSF inhalation bioaccessibility test and UBM bioaccessibility protocol (based on an operational chemical methodology mimicking soil ingestion and its residence in the gastrointestinal tract of the human body). These analyses revealed 2 groups of samples with distinct behavior. The first group of samples presents relatively stable bearing phases, mainly found in the residual fraction (As and Pb), presenting only a low health risk (very low bioaccessible). The second group consists of Cd and/or Zn-bearing phases, mainly labile (resulting from dissolution/precipitation phenomena), while gastric bioaccessibility reaches more than 85%. Note that Pb, Cd, and Zn have the potential to cause non-carcinogenic risks to children and As and Pb present a carcinogenic risk for children and adults even if only the bioaccessible fraction is considered. It has therefore been shown that the meteoric alteration of the tailing induces a change in speciation leads to an increase in environmental and health risks. These results are essential because they highlight the need for an integrated approach in order to clearly highlight the presence of risks but also that this approach will allow a better understanding of the potential rehabilitation path of this site.

Environmental impact assessment of industrial activities on heavy metals distribution in street dust and soil.

Street dust and soil are important materials for evaluating the contaminants level in industrial areas. Detailed size-resolved distribution of metal(loid)s in street dusts and soils influenced by industrial activities has rarely been investigated. This study was carried out to understand how industrialization might affect the size distribution of metal(loid)s concentration and contamination level in the street dust and soil from Murcia, southern Spain. An industrial and a natural areas were selected and surface soil and street dust samples were taken. They were fractionated into eleven size classes and total concentrations of Pb, Zn, Cu, Cd, Cr, Ni, As and Fe were determined in both the bulk samples and their fractions. Enrichment factor, geoaccumulation index, and mass loading of different heavy metal(loids) were calculated. The results indicated that the street dust from natural and industrial areas had almost the same particle size distribution, both containing higher percentage of coarse-sized particles than the soil. Industrialization seems to have only slightly affected the concentration of most elements studied in the soil. In contrast, the concentrations of the heavy elements in bulk industrial dust samples and all their size fractions were extremely higher than those from the natural area. This means that the industrial activities only affected the size dependency of the concentration (contamination level) of certain elements (Pb, Zn, Cu, Cd, and Cr) in the street dust, but not in the soil.

Effect of land use and soil properties in the feasibility of two sequential extraction procedures for metals fractionation.

Several sequential extraction procedures are widely applied for metals chemical fractionation in the literature. However, their limitations to be used in different soils and metals have not been discussed in detail. This study compares two of the most commonly used extraction methods for metals chemical fractionation: Tessier and BCR. The objectives were to i) assess the differences between concentrations of metals extracted in each fraction by both Tessier and BCR procedures; ii) elucidate if soil properties affected the extraction ability of each fraction from both procedures; and iii) evaluate how land use contributes to different chemical metal distribution. Results indicated that both methods provide similar results when were applied to the same soil, since non-significant differences were found in metal concentrations between both methods at each fraction. Conversely, when we compared among land uses, significant differences were found in the metal concentration between both methods, especially between agricultural/urban/industrial against forest soil. Redundancy analysis showed that in carbonate-rich soils, BCR extraction method could cover up the real concentration of exchangeable metals with those bound to the carbonate phase, being the Tessier method the most suitable one for this kind of soils. Therefore, although sequential extraction is a useful tool to understand the distribution of metals in soil, the method used must be selected according to the land use and specific soil characteristics, taking into account at least, soil carbonate content.

Atmospheric dust characterisation in the mining district of Cartagena-La Unión, Spain: Air quality and health risks assessment.

Nowadays, air pollution has a major impact on the environment and human health. Owen gauges allow the sampling of atmospheric depositions in polluted sites for further characterisation. This paper shows the study of the air particles of an old mining zone in Cartagena-La Unión (South-east of Spain) in order to quantify their potential risk on human health. There were 4 strategic sites monitored: the main mining tailing (Avenque), the urban area (La Unión), an agricultural zone (formerly mining) and a site in the Mediterranean coast. Physico-chemical and mineralogical characterisation was applied to atmospheric fallouts. The granulometry revealed a dust particle size around 15 µm, with the coarsest particles in the urban area and the thinnest at the tailing site. XRD analyses showed the presence of quartz, carbonates, sulphides and sulphates. Observations with SEM-EDX confirmed chemical spectra and allowed us to classify the particles into well-crystallised minerals and heterogeneous dusts. Total metal content determination was carried out by ICP-MS analyses and results showed Zn, Pb, As and Cd fluxes (respectively 2549, 1275, 68 and 7 µg·m-2·d-1) exceeding the limit values set by European legislations in the mining area. The fluxes of Zn, Pb and As also exceed these standards in the urban area whereas the coastal zone only exceeds the thresholds in the case of As. Inhalation health risk (defined by US EPA, 2009) was quantified in the sites using total and bioaccessible metal contents of the dusts. Risk calculations using total metal content considering a residential scenario showed acceptable risk for all sites except for the mining tailing which presented non-acceptable cancer and hazard risk mainly due to the total As and Pb contents. When considering the bioaccessible fraction of As and Pb, the risk diminished to acceptable values, demonstrating the overestimation produced when using total metal contents.

Provenance and environmental risk of windblown materials from mine tailing ponds, Murcia, Spain.

Atmospheric particulates play a vital role in the transport of potentially toxic metals, being an important exposure pathways of people to toxic elements, which is faster and can occur in a much larger scale than water, soil and biota transport. Windblown materials in abandoned tailing ponds have not been well examined. The objectives of this investigation were: to study the major physical and geochemical properties of the materials eroded by wind inside the tailing ponds, and to understand the relative contribution of different sources to its heavy metals concentration. Study area is located in Cartagena-La Union mining district (SE Spain), where metallic mining of Fe, Pb and Zn has been developed for more than 2500 years. Wind-eroded particulates were monthly collected at 3 different heights (20, 50, and 80 cm) from the ground for a period of a full year using 4 dust collectors. Four tailing samples and 4 surface soil samples from the surrounding hills were also taken. Dust, soil, and tailing samples were examined for pH, particle size distribution, electrical conductivity, calcium carbonate content, Pb, Cu, Zn, Cd, Mn, Co, Ni, Ti and Zr concentrations. The results indicated that very coarse textured, slightly saline, and almost neutral wind-eroded deposits were generated with a very high temporal variability throughout the year. They also showed that the concentration of Cd, Mn, Pb and Zn, in the dust samples is extraordinarily high (18, 1254, 1831, and 5747 mg kg-1 respectively), whereas Co, Ni, and Cu had concentrations into the range of background concentrations found in the Earth's crust (3.8, 12, and 60 mg kg-1 respectively). Besides, the concentration of both categories of heavy metals in the dust samples was higher than that in tailing and less than that of the soils. The barren surfaces of tailing ponds and also the surface soils of the surrounding area seem to be the major contributors to the dust collected. Therefore, abandoned mines as well as their tailing ponds should be rehabilitated by proper technologies and then well stabilized and/or covered by appropriate plant vegetation to control the transfer, particularly by air, of environmentally hazardous materials to other areas.

Greenhouse gas emissions and soil organic matter dynamics in woody crop orchards with different irrigation regimes.

Water scarcity in arid, semiarid and dry regions is a limiting factor for the development of sustainable agriculture. As a consequence, the adoption of new strategies such as regulated deficit irrigation (RDI) to reduce water and energy consumption will be essential. Decreases in irrigation water content may also have positive effects on soil C cycle. Thus, an experiment was setup in three woody crop orchards during two years, with the objective of assessing if RDI can reduce soil CO2 and N2O emissions, modify soil inorganic C and organic C quality and stability and affect soil aggregation. Soil CO2 and N2O emissions were measured every two weeks while soil samplings were carried out every three months. Results indicated that decreases in soil moisture by RDI implementation were related to significant decreases in CO2 emissions in all crops. RDI contributed to an average decrease, compared with full irrigation, of 1088-1664 g CO2 m-2 in the experimental period. Furthermore, CO2 emission was negatively correlated with inorganic C, suggesting the protective effect of soil carbonates towards organic matter. RDI also contributed to significantly decrease soil N2O emissions. However, N2O emission patterns did not directly follow soil moisture patterns and were constant in the experimental period. RDI contributed to an average decrease, compared with full irrigation, of 90-409 mg N2O m-2. No physicochemical property was significantly affected by irrigation regime. Although microbial biomass was not significantly affected by RDI, ß-glucosidase activity was significantly higher under full irrigation during the warm seasons, with significant positive correlation with CO2 emissions. This seems to suggest that a significant fraction of CO2 emitted from soil derives from organic matter degradation, which is limited with low water content. So, RDI could contribute to promote soil C sequestration by reduced greenhouse gas emissions, with no negative effects on soil structure at short-term.

Bioaugmentaton in Technosols created in abandoned pyritic tailings can contribute to enhance soil C sequestration and plant colonization.

Creation of Technosols in combination with phytostabilization may be a sustainable strategy to minimize the environmental and human health hazards derived from mine tailings. Bioaugmentation can facilitate plant establishment and growth for efficient phytostabilization. In order to assess if bioaugmentation can increase soil quality and fertility, decrease metal(loid) mobility and accelerate plant colonization, a one-year field experiment was designed with creation of Technosols in two tailings ponds with different pH (acidic (AT) and neutral (NT)), with addition of marble waste (MaW) and two organic materials (pig manure (PM) and sewage sludge (SS), without or with inoculation of effective microorganisms (EM) at three rates. Results showed that MaW was the main factor responsible for maintaining pH ~7 in AT and ~8 in NT, decreasing salinity, and decreasing the soluble fraction of metals (70-99%). The soluble fraction of As decreased ~45% in AT, related to increases in pH up to neutrality, while increased ~90% in NT with PM due to pH>8 and higher content of organic compounds. The addition of PM and SS significantly increased soil organic C (SOC), nutrient contents and microbial biomass and activity in both tailings, being PM more effective. However, a positive priming effect was observed in NT with SS addition likely due to higher C/N ratio and lack of nutrients. There was a significant effect of EM rate on inorganic C, SOC, N, K and microbial biomass and activity, with higher values as rate increased. Vegetation richness and density directly increased with increasing EM rate. Multivariate analyses showed that the most important properties contributing to increase richness and plant density were microbial biomass and N. Thus, bioaugmentation contributed to soil C sequestration (as organic and inorganic C) and soil fertility, related to high soil microbial biomass and activity, which facilitated an effective colonization of vegetation.

Carbon mineralization, microbial activity and metal dynamics in tailing ponds amended with pig slurry and marble waste.

A field experiment was set up in Cartagena-La Unión Mining District, SE Spain, aimed at evaluating the short-term effects of pig slurry (PS) amendment alone and together with marble waste (MW) on organic matter mineralization, microbial activity and stabilization of heavy metals in two tailing ponds. These structures pose environmental risk owing to high metals contents, low organic matter and nutrients, and null vegetation. Carbon mineralization, exchangeable metals and microbiological properties were monitored during 67 d. The application of amendments led to a rapid decrease of exchangeable metals concentrations, except for Cu, with decreases up to 98%, 75% and 97% for Cd, Pb and Zn, respectively. The combined addition of MW+PS was the treatment with greater reduction in metals concentrations. The addition of PS caused a significant increase in respiration rates, although in MW+PS plots respiration was lower than in PS plots. The mineralized C from the pig slurry was low, approximately 25-30% and 4-12% for PS and MW+PS treatments, respectively. Soluble carbon (Csol), microbial biomass carbon (MBC) and ß-galactosidase and ß-glucosidase activities increased after the application of the organic amendment. However, after 3d these parameters started a decreasing trend reaching similar values than control from approximately day 25 for Csol and MBC. The PS treatment promoted highest values in enzyme activities, which remained high upon time. Arylesterase activity increased in the MW+PS treatment. Thus, the remediation techniques used improved soil microbiological status and reduced metal availability. The combined application of PS+MW reduced the degradability of the organic compounds.