Harnessing photosynthetic microorganisms for enhanced bioremediation of microplastics: A comprehensive review.

Mismanaged plastics, upon entering the environment, undergo degradation through physicochemical and/or biological processes. This process often results in the formation of microplastics (MPs), the most prevalent form of plastic debris (<1 mm). MPs pose severe threats to aquatic and terrestrial ecosystems, necessitating innovative strategies for effective remediation. Some photosynthetic microorganisms can degrade MPs but there lacks a comprehensive review. Here we examine the specific role of photoautotrophic microorganisms in water and soil environments for the biodegradation of plastics, focussing on their unique ability to grow persistently on diverse polymers under sunlight. Notably, these cells utilise light and CO2 to produce valuable compounds such as carbohydrates, lipids, and proteins, showcasing their multifaceted environmental benefits. We address key scientific questions surrounding the utilisation of photosynthetic microorganisms for MPs and nanoplastics (NPs) bioremediation, discussing potential engineering strategies for enhanced efficacy. Our review highlights the significance of alternative biomaterials and the exploration of strains expressing enzymes, such as polyethylene terephthalate (PET) hydrolases, in conjunction with microalgal and/or cyanobacterial metabolisms. Furthermore, we delve into the promising potential of photo-biocatalytic approaches, emphasising the coupling of plastic debris degradation with sunlight exposure. The integration of microalgal-bacterial consortia is explored for biotechnological applications against MPs and NPs pollution, showcasing the synergistic effects in wastewater treatment through the absorption of nitrogen, heavy metals, phosphorous, and carbon. In conclusion, this review provides a comprehensive overview of the current state of research on the use of photoautotrophic cells for plastic bioremediation. It underscores the need for continued investigation into the engineering of these microorganisms and the development of innovative approaches to tackle the global issue of plastic pollution in aquatic and terrestrial ecosystems.

Microplastic interactions in the agroecosystems: methodological advances and limitations in quantifying microplastics from agricultural soil.

The instantaneous growth of the world population is intensifying the pressure on the agricultural sector. On the other hand, the critical climate changes and increasing load of pollutants in the soil are imposing formidable challenges on agroecosystems, affecting productivity and quality of the crops. Microplastics are among the most prevalent pollutants that have already invaded all terrestrial and aquatic zones. The increasing microplastic concentration in soil critically impacts crop plants growth and yield. The current review elaborates on the behaviors of microplastics in soil and their impact on soil quality and plant growth. The study shows that microplastics alter the soil's biophysical properties, including water-holding capacity, bulk density, aeration, texture, and microbial composition. In addition, microplastics interact with multiple pollutants, such as polyaromatic hydrocarbons and heavy metals, making them more bioavailable to crop plants. The study also provides a detailed insight into the current techniques available for the isolation and identification of soil microplastics, providing solutions to some of the critical challenges faced and highlighting the research gaps. In our study, we have taken a holistic, comprehensive approach by analysing and comparing various interconnected aspects to provide a deeper understanding of all research perspectives on microplastics in agroecosystems.

The impact of olive mill wastewater on soil properties, nutrient and heavy metal availability - A study case from Syrian vertisols.

Olive oil mill wastewater (OMW) is an environmental concern in olive oil producers' regions due to its use in agricultural soils as an organic amendment. However, OMW can also be used as organic fertilizer due to their high organic matter and nutrient levels, but its use, when it occurs without environmental management, can cause serious environmental implications for soils and waters. This work evaluated the impact of different OMW levels on a set of physicochemical parameters from an agricultural vertisol where wheat grew (Triticum aestivum L var. Douma 1). A set of physicochemical parameters were conducted before adding different levels of OMW (0, 5, 10 and 15 L m-2) at two soil depths (0-30 and 30-60 cm) and for the two growing seasons to determine: i) the effect of OMW treatments on the studied physicochemical soil properties (bulk density, soil porosity, soil pH, electrical conductivity and organic matter), ii) available primary (N, P, K) and secondary macronutrients (Ca, Mg and Na), ii) micronutrients (Cu Fe, Mn and Zn), and iv) available heavy metals (Cd and Pb). The results indicated that soil physicochemical parameters were slightly improved, mainly due to improvement in organic matter, macro- and micronutrients, usually proportionally to the olive mill wastewater dose. Cadmium and Pb were within the permissible limits. The increased OMW had different behaviour on the soil nutritional balances of different elements, leading to nutrient imbalances, although in some cases, they were improved. However, the plant growth was not affected, and it was improved under 10 L m-2 and 15 L m-2 doses. The results offer valuable data about the use of OMW as organic fertilizer for crops and their potential impact on soil properties.

Use of metal nanoparticles in agriculture. A review on the effects on plant germination.

Agricultural nanotechnology has become a powerful tool to help crops and improve agricultural production in the context of a growing world population. However, its application can have some problems with the development of harvests, especially during germination. This review evaluates nanoparticles with essential (Cu, Fe, Ni and Zn) and non-essential (Ag and Ti) elements on plant germination. In general, the effect of nanoparticles depends on several factors (dose, treatment time, application method, type of nanoparticle and plant). In addition, pH and ionic strength are relevant when applying nanoparticles to the soil. In the case of essential element nanoparticles, Fe nanoparticles show better results in improving nutrient uptake, improving germination, and the possibility of magnetic properties could favor their use in the removal of pollutants. In the case of Cu and Zn nanoparticles, they can be beneficial at low concentrations, while their excess presents toxicity and negatively affects germination. About nanoparticles of non-essential elements, both Ti and Ag nanoparticles can be helpful for nutrient uptake. However, their potential effects depend highly on the crop type, particle size and concentration. Overall, nanotechnology in agriculture is still in its early stages of development, and more research is needed to understand potential environmental and public health impacts.

Adsorption of antibiotics on bio-adsorbents derived from the forestry and agro-food industries.

Antibiotic consumption at high levels in both human and veterinary populations pose a risk to their eventual entry into the food chain and/or water bodies, which will adversely affect the health of living organisms. In this work, three materials from forestry and agro-food industries (pine bark, oak ash and mussel shell) were investigated as regards their potential use as bio-adsorbents in the retention of the antibiotics amoxicillin (AMX), ciprofloxacin (CIP) and trimethoprim (TMP). Batch adsorption/desorption tests were conducted, adding increasing concentrations of the pharmaceuticals individually (from 25 to 600 µmol L-1), reaching maximum adsorption capacities of ≈ 12000 µmol kg-1 for the three antibiotics, with removal percentages of ≈ 100% for CIP, 98-99% adsorption for TMP onto pine bark, and 98-100% adsorption for AMX onto oak ash. The presence of high calcium contents and alkaline conditions in the ash favored the formation of cationic bridges with AMX, whereas the predominance of hydrogen bonds between pine bark and TMP and CIP functional groups explain the strong affinity and retention of these antibiotics. The Freundlich's model provided the best prediction for AMX adsorption onto oak ash and mussel shell (heterogeneous adsorption), whereas the Langmuir's model described well AMX adsorption onto pine bark, as well as CIP adsorption onto oak ash (homogeneous and monolayer adsorption), while all three models provided satisfactory results for TMP. In the present study, the results obtained were crucial in terms of valorization of these adsorbents and their subsequent use to improve the retention of antibiotics of emerging concern in soils, thereby preventing contamination of waters and preserving environment quality.

Clarithromycin as soil and environmental pollutant: Adsorption-desorption processes and influence of pH.

Antibiotics pollution is a growing environmental issue, as high amounts of these compounds are found in soil, water and sediments. This work studies the adsorption/desorption of the macrolide antibiotic clarithromycin (CLA) for 17 agricultural soils with different edaphic characteristics. The research was carried out using batch-type experiments, with an additional assessment of the specific influence of pH for 6 of the soils. The results show that CLA adsorption reaches between 26 and 95%. In addition, the fit of the experimental data to adsorption models provided values between 1.9 and 19.7 Ln µmol1-n kg-1 for the KF, Freundlich affinity coefficient, and between 2.5 and 10.5 L kg-1 for Kd, distribution constant of Linear model. Regarding the linearity index, n, it varied between 0.56 and 1.34. Desorption showed lower scores than adsorption, with an average of 20%, and with values of 3.1 and 93.0 Ln µmol1-n kg-1 for KF(des) and 4.4 and 95.0 L kg-1 for Kd(des). The edaphic characteristics with the highest influence on adsorption were the silt fraction content and the exchangeable Ca content, while in the case of desorption, they were the total nitrogen, organic carbon, and exchangeable Ca and Mg contents. Regarding the pH, within the range studied (between 3 and 10), its value did not decisively affect the adsorption/desorption process. Overall, the set of these results could be of help to program appropriate measures leading to the retention/elimination of this antibiotic when it reaches the environment as a pollutant.

The forgotten impacts of plastic contamination on terrestrial micro- and mesofauna: A call for research.

Microplastics (MP) and nanoplastics (NP) contamination of the terrestrial environment is a growing concern worldwide and is thought to impact soil biota, particularly the micro and mesofauna community, by various processes that may contribute to global change in terrestrial systems. Soils act as a long-term sink for MP, accumulating these contaminants and increasing their adverse impacts on soil ecosystems. Consequently, the whole terrestrial ecosystem is impacted by microplastic pollution, which also threatens human health by their potential transfer to the soil food web. In general, the ingestion of MP in different concentrations by soil micro and mesofauna can adversely affect their development and reproduction, impacting terrestrial ecosystems. MP in soil moves horizontally and vertically because of the movement of soil organisms and the disturbance caused by plants. However, the effects of MP on terrestrial micro-and mesofauna are largely overlooked. Here, we give the most recent information on the forgotten impacts of MP contamination of soil on microfauna and mesofauna communities (protists, tardigrades, soil rotifers, nematodes, collembola and mites). More than 50 studies focused on the impact of MP on these organisms between 1990 and 2022 have been reviewed. In general, plastic pollution does not directly affect the survival of organisms, except under co-contaminated plastics that can increase adverse effects (e.g. tire-tread particles on springtails). Besides, they can have adverse effects at oxidative stress and reduced reproduction (protists, nematodes, potworms, springtails or mites). It was observed that micro and mesofauna could act as passive plastic transporters, as shown for springtails or mites. Finally, this review discusses how soil micro- and mesofauna play a key role in facilitating the (bio-)degradation and movement of MP and NP through soil systems and, therefore, the potential transfer to soil depths. More research should be focused on plastic mixtures, community level and long-term experiments.

Health risk assessment of the European inhabitants exposed to contaminated ambient particulate matter by potentially toxic elements.

PM10-associated potential toxic elements (PTEs) can enter the respiratory system and cause health problems. In the current study, the health risk indices caused by PM10 inhalation by adults, children, and infants in 158 European cities between 2013 and 2019 were studied to determine if Europeans were adversely affected by carcinogenic and non-carcinogenic factors or not. The Mann-Kendall trend test examined PM10's increasing or decreasing trend. Random Forest analysis was also used to analyse meteorological factors affecting PM10 in Europe. Hazard quotient and cancer risk were estimated using PM10-associated PTEs. Our results showed a decline in continental PM10 concentrations. The correlation between PM10 concentrations and temperature (-0.40), PBLH (-0.39), and precipitation were statistically strong (-0.21). The estimated Pearson correlation coefficients showed a statistically strong positive correlation between As & Pb, As & Cd, and Cd & Pb during 2013-2019, indicating a similar origin. PTEs with hazard quotients below one, regardless of subpopulation type, posed no noncancerous risk to Europeans. The hazard quotient values positively correlated with time, possibly due to elevated PTE levels. In our study on carcinogen pollution in Europe between 2013 and 2019, we found unacceptable levels of As, Cd, Ni, and Pb among adults, children, and infants. Carcinogenic risk rates were highest for children, followed by infants, adult women, and adult men. Therefore, besides monitoring and mitigating PM concentrations, effective control of PM sources is also needed.

Use of Three Different Nanoparticles to Reduce Cd Availability in Soils: Effects on Germination and Early Growth of Sinapis alba L.

Globally, cadmium (Cd) is one of the metals that causes the most significant problems of contamination in agricultural soils and toxicity in living organisms. In this study, the ability of three different nanoparticles (dose 3% w/w) (hydroxyapatite (HANPs), maghemite (MNPs), or zero-valent iron (FeNPs)) to decrease the availability of Cd in artificially contaminated agricultural soil was investigated. The effect of Cd and nanoparticles on germination and early growth of Sinapis alba L. was also assessed by tolerance/toxicity bioassays. The available Cd contents in the contaminated soil decreased after treatment with the nanoparticles (available Cd decreased with HANPs: >96.9%, MNPs: >91.9%, FeNPs: >94%), indicating that these nanoparticles are highly efficient for the fixation of available Cd. The toxicity/tolerance bioassays showed different behavior for each nanoparticle. The HANPs negatively affected germination (G(%): 20% worsening compared to control soil), early root growth (Gindex: -27.7% compared to control soil), and aerial parts (Apindex: -12%) of S. alba, but showed positive effects compared to Cd-contaminated soils (Gindex: +8-11%; Apindex: +26-47%). MNP treatment in Cd-contaminated soils had a positive effect on germination (G(%): 6-10% improvement) and early growth of roots (Gindex: +16%) and aerial parts (Apindex: +16-19%). The FeNPs had a positive influence on germination (G(%): +10%) and growth of aerial parts (Apindex: +12-16%) but not on early growth of roots (Gindex: 0%). These nanoparticles can be used to reduce highly available Cd contents in contaminated soils, but MNPs and FeNPs showed the most favorable effects on the early growth and germination of S. alba.

Metabolic and genetic derangement: a review of mechanisms involved in arsenic and lead toxicity and genotoxicity.

Urbanisation and industrialisation are on the rise all over the world. Environmental contaminants such as potentially toxic elements (PTEs) are directly linked with both phenomena. Two PTEs that raise greatest concern are arsenic (As) and lead (Pb) as soil and drinking water contaminants, whether they are naturally occurring or the consequence of human activities. Both elements are potential carcinogens. This paper reviews the mechanisms by which As and Pb impair metabolic processes and cause genetic damage in humans. Despite efforts to ban or limit their use, due to high persistence both continue to pose a risk to human health, which justifies the need for further toxicological research.

Elucidating of potentially toxic elements contamination in topsoils around a copper smelter: Spatial distribution, partitioning and risk estimation.

Soil pollution by potentially toxic elements (PTEs) as one of the major environmental hazards is associated with metal exploration and refining acting. In this study, forty-five topsoil samples surrounding a copper smelter factory were taken and analysed using standard routine methods. The total concentration, chemical fractionation and the mobility potential of As, Cd, Cr, Cu, Pb and Zn were analysed. Additionally, the spatial distribution of PTEs, the potential ecotoxicological, and human health risks was assessed. The range of total Cu was 1478-4718 mg kg-1, reaching up to 501.5, 21.6, 118.4, 573.5 and 943.3 mg kg-1 for total contents of As, Cd, Cr, Pb and Zn, respectively. The potentially available fractions after sequential extraction reveal all studied PTE were dramatically mobile and available in the studied area (86%, 69.3%, 59.5%, 87.2%, 84% and 68% for As, Cd, Cr, Pb, Zn and Cu, respectively), reflecting that the concentration and accumulation of these elements are profoundly affected or originated by smelting activities and deposition of atmospheric emissions of the Cu smelting factory. The spatial distribution of all PTEs indicated that concentrations of these element near the smelter Cu-factory were elevated. Accordingly, the ecotoxicology status of the studied area suggests that significantly high risks are posed by the measured PTEs. Non-carcinogenic effects of As, Pb and Cu were significantly much higher than the recommended value (HI = 1), suggesting that these three PTEs could adversely impact children's health. For adults, only the HI value of As was greater than one.

Nano-Fe2O3 as a tool to restore plant growth in contaminated soils - Assessment of potentially toxic elements (bio)availability and redox homeostasis in Hordeum vulgare L.

This work aimed to evaluate the potential of Fe2O3 nanoparticles (nano-Fe2O3) to alleviate potentially toxic elements (PTEs) - induced stress in barley plants (Hordeum vulgare L.), focusing on bioaccumulation patterns and on plant growth and redox homeostasis. To achieve this goal, plants grew in two agricultural soils, contaminated by different levels of PTEs, collected from an industrial area, previously amended, or not, with 1% (w/w) nano-Fe2O3. After 14 d of growth, biometric parameters were evaluated, along with the analysis of PTEs bioaccumulation and biochemical endpoints. After exposure to contaminated soils, plant development was greatly affected, as evidenced by significant decreases in root length and biomass production. However, upon co-treatment with nano-Fe2O3, lower inhibitory effects on biometric parameters were observed. Regarding the oxidative damage, both soils led to increases in lipid peroxidation and superoxide anion concentration, though hydrogen peroxide levels were only increased in the most contaminated soil. In general, these changes in the oxidative stress markers were accompanied by an upregulation of different antioxidant mechanisms, whose efficiency was even more powerful upon soil amendment with nano-Fe2O3, thus lowering PTEs-induced oxidative damage. Altogether, the present study revealed that nano-Fe2O3 can protect the growth of barley plants under contaminated soils.

Soils from abandoned shooting range facilities as contamination source of potentially toxic elements: distribution among soil geochemical fractions.

Civilian and military shooting range facilities cause environmental issues in several countries due to the accumulation of Potentially Toxic Elements; as a result of weathering of ammunitions accumulated into the soils. The contents and distribution of Cu, Ni, Pb and Zn were analyzed in 12 soils in an abandoned clay target shooting range at two different depths (0-15 and 15-30 cm). Single extractions (CaCl2 and DTPA) and Tessier sequential extraction were conducted to assess the PTE mobility and the PTE distribution in the different soil geochemical fractions at both depths. High total contents of Pb were found at both soil depths, while Cu, Ni and Zn showed lower significance levels. Copper, Ni and Zn are mainly associated with the residual fraction (> 95% of total content in all cases). However, Pb was highly associated with exchangeable fractions (21-52%), showing a high mobility at both depths. With moderate-high contents of organic matter (6-12%), the studied soils have acidic values and low levels of Al, Fe and Mn oxides that favors the migration of Pb through the soil profile and potential transformation to more mobile forms (Pb0 to Pb2+ and Pb4+). Although Pb reduced downward mobility in soils, due to the specific conditions of these facilities and the lead source (weathering of ammunition), risk assessment studies on clay-target shooting and firing range facilities should study the potential migration of Pb through the soil profile.

Assessment of iron-based and calcium-phosphate nanomaterials for immobilisation of potentially toxic elements in soils from a shooting range berm.

Shooting range facilities in military areas have been indicated as a hotspot of land degradation with high contents of Potentially Toxic Elements (PTEs). Currently, based on the new nanomaterials with specific characteristics, nanoremediation technologies are used to immobilise and to reduce the availability of PTEs in field and laboratory conditions. In this study, the effects of nano-hydroxyapatite and/or hematite on PTEs immobilisation (As, Cd, Cu, Pb, Sb and Zn) in military shooting range soils were assessed through the measure of available and leachable forms with three single-extractions: calcium chloride (0.01M CaCl2), low molecular weight organic acids (10 mM LMWOAs) and toxicity characteristic leaching procedure (TCLP). A sequential chemical extraction was used to determine the distribution of the PTEs in the different geochemical phases of the soils before and after the nanomaterial treatments. Results showed that the availability of PTEs decreased, especially for Pb (40-95%) and Zn (50-99%) after nanomaterial treatments. When both nanomaterial (hydroxyapatite + hematite) were combined, the immobilisation rate improved. However, when each nanomaterial was added individually to the soils, some elements, such as, Cu or Sb, showed a slight increment of their mobilisation. The sequential chemical extraction showed that the highest percentage of PTEs were mainly in the residual fraction before and after adding nanomaterials, being even higher in soils after the nanomaterial treatments. Likewise, the mobile fractions decreased after the treatment with nanomaterials. Our findings suggest that nanoremediation techniques improve the soil conditions, but they should be used carefully to avoid mobilisation of non-target PTEs or unexpected potentially impacts for soil biota.

Chemical availability versus bioavailability of potentially toxic elements in mining and quarry soils.

Abandoned mining and quarry areas are sources of potentially toxic elements (PTEs), through lixiviates or transfer processes of bioavailable fractions from mining wastes and tailings. In this study, earthworms (Eisenia fetida Savigny, 1826) were exposed for 28 days to two mining soils from a lead/zinc mine and two quarry soils from an old serpentine quarry. Despite their pseudo total metal contents, a previous characterization of these soils pointed out for a low chemical availability of PTEs. Therefore, a multibiomarker approach was used and the response of E. fetida to soils was assessed through the analysis of neurotoxic, oxidative stress, energy metabolism and DNA damage biomarkers (acetylcholinesterase, catalase, glutathione-s-transferase, lactate dehydrogenase, lipid peroxidation and DNA strand breaks). Metal bioaccumulation was also assessed to evaluate bioavailability and organism's exposure. Results showed that high contents of PTEs were recorded in the whole body of earthworms exposed to lead/zinc mine. However, the bioaccumulation factors for worms exposed to soils from both sampling sites were <1 due to the high PTEs contents in soils. Earthworms exposed to both types of soils displayed neurotoxic and energy metabolism effects. However, significant levels of oxidative stress and DNA damage were recorded only for earthworms exposed to lead/zinc mine soils. This study demonstrated that despite the low availability of PTEs showed by previous sequential chemical extractions, the results obtained from the direct toxicity assessment performed in this study, highlight the importance of a multibiomarker approach using soil organisms to provide a better evaluation of soils pollution.

Ability of Cytisus scoparius for phytoremediation of soils from a Pb/Zn mine: Assessment of metal bioavailability and bioaccumulation.

Abandoned mining areas are an environmental concern for aquatic and terrestrial ecosystems due to their unfavourable soil properties and high levels of potentially toxic elements. Despite this, some plant species may grow spontaneously and colonise these areas; being suitable in many cases for restoration practices, since they may accumulate metals in their tissues. This study aims to assess the effectiveness of 14 chemical soil extractants to predict the bioavailability of toxic elements (Cd, Pb and Zn) in soils from the abandoned Pb/Zn mine of Rubiais (NW Spain), based on root and shoot metal contents in Cytisus scoparius (L.) Link, which grows spontaneously in this area. Afterwards, its potential for phytoremediation activities was assessed. Mine soils showed high contents Cd (1.77-14.38 mg kg-1), Pb (850-2137 mg kg-1) and Zn (1754-12090 mg kg-1). Cytisus scoparius grows in spite of these high metal contents; accumulating Zn and Pb in its roots, Zn in the aerial part and excluding mostly Cd from its tissues. None of the extractants used to determine the bioavailable content of Pb allow predicting its availability for C. scoparius. However, LMWOA was the most effective extractant to determine the bioavailability of Cd and Zn for this species. Besides, NH4NO3 and Ca(NO3)2 are also good indicators for Zn bioavailability. The analysis of bioconcentration and translocation factors suggest that C. scoparius behaves like a Zn accumulator plant, whereas alternatively, it behaves like a Pb phytostabiliser and as a Cd excluder species. Thus, C. scoparius can be used as a species for mine soil restoration, decreasing the mobility of metals and preventing their dispersion to another ecosystem compartments.

Oxidative stress, energy metabolism and molecular responses of earthworms (Eisenia fetida) exposed to low-density polyethylene microplastics.

Soils are both a sink and a pathway of plastic wastes, but there is a great lack of knowledge regarding their impacts on soil biota. To tackle the mechanisms of toxicity of these contaminants to soil invertebrates, earthworms (Eisenia fetida Savigny, 1826) were exposed during 28 days to different concentrations of low-density polyethylene microplastics (62, 125, 250, 500 and 1000 mg MPs kg-1 soildw) with sizes ranging between 250 and 1000 µm, in an artificial soil. The ecotoxicological responses were evaluated by analysing various oxidative stress biomarkers (catalase, glutathione S-transferase and thiobarbituric acid reactive substances), a biomarker of energy metabolism (lactate dehydrogenase) and overall organism molecular changes by Fourier transform infrared spectrometry (FTIR) and nuclear magnetic resonance (NMR) analyses. Significant effects resulting from an unbalanced oxidative stress system, expressed in terms of thiobarbituric acid reactive substances levels were recorded on earthworms exposed at the three highest concentrations tested. Despite that, no significant changes were recorded on the molecular profiles of earthworms by FTIR-ATR. NMR analysis pointed out for differences from the control, only for earthworms exposed to the lowest concentration of MPs. Considering that stress responses are complex, and involve multiple mechanisms, a cluster analysis taking into account all the parameters assessed, clearly identified two groups of earthworms separated by the concentration of 250 mg MPs kg-1 soildw, above each meaningful effects were recorded.

Pb pollution in soils from a trap shooting range and the phytoremediation ability of Agrostis capillaris L.

Pb pollution caused by shooting sport activities is a serious environmental problem that has increased considerably in recent decades. The aims of this study were firstly to analyze Pb pollution in soils from a trap shooting range abandoned in 1999, secondly to study the effectiveness of different extractants [CaCl2, DTPA, NH4OAc, low molecular weight organic acids (LMWOA), and bidistilled water (BDW)] in order to determine Pb bioavailability in these soils, and finally to evaluate the phytoremediation ability of spontaneous vegetation (Agrostis capillaris L.). To this end, 13 soils from an old trap shooting range (Galicia, NW Spain) were studied. It was found that Pb levels in the soils were higher than 100 mg kg(-1), exceeding the generic reference levels, and three of these samples even exceeded the USEPA threshold level (400 mg kg(-1)). In general, the reagent that best represents Pb bioavailability and has the greatest extraction efficiency was CaCl2, followed by DTPA, NH4OAc, LMWOA, and BDW. A. capillaris Pb contents ranged between 9.82 and 1107.42 mg kg(-1) (root) and between 6.43 and 135.23 mg kg(-1) (shoot). Pb accumulation in roots, as well as the presence of secondary mineral phases of metallic Pb in the adjacent soil, showed the phytostabilization properties of A. capillaris.

Identifying sources of Pb pollution in urban soils by means of MC-ICP-MS and TOF-SIMS.

Lead pollution was evaluated in 17 urban soils from parks and gardens in the city of Vigo (NW Spain). The Pb isotope ratios ((207)Pb/(206)Pb, (208)Pb/(204)Pb, (206)Pb/(204)Pb and (208)Pb/(206)Pb) were determined after being measured by MC-ICP-MS. The association of the isotopes ((204)Pb, (206)Pb, (207)Pb and (208)Pb) with the different components of the soil was studied using TOF-SIMS. The isotopic ranges obtained for the samples were between 1.116 and 1.203 ((206)Pb/(207)Pb), 2.044-2.143 ((208)Pb/(206)Pb), 37.206-38.608 ((208)Pb/(204)Pb), 15.5482-15.6569 ((207)Pb/(204)Pb) and 17.357-18.826 ((206)Pb/(204)Pb). The application of the three-end-member model indicates that the Pb derived from petrol is the main source of Pb in the soils (43.51% on average), followed by natural or geogenic Pb (39.12%) and industrial emissions (17.37%). The emissions derived from coal combustion do not appear to influence the content of Pb in the soil. TOF-SIMS images show that the Pb mainly interacts with organic matter. This technique contributes to the understanding of the association of anthropogenic Pb with the components of the soil, as well as the particle size of these associations, thus allowing the possible sources of Pb to be identified.