Bioavailability and extraction of heavy metals from contaminated soil by Atriplex halimus

Pot experiments were performed to evaluate the phytoremediation capacity of plants of Atriplex halimus grown in contaminated mine soils and to investigate the effects of organic amendments on the metal bioavailability and uptake of these metals by plants. Soil samples collected from abandoned mine sites north of Madrid (Spain) were mixed with 0, 30 and 60 Mg ha?1 of two organic amendments, with different pH and nutrients content: pine-bark compost and horse- and sheep-manure compost. The increasing soil organic matter content and pH by the application of manure amendment reduced metal bioavailability in soil stabilising them. The proportion of Cu in the most bioavailable fractions (sum of the water-soluble, exchangeable, acid-soluble and Fe?Mn oxides fractions) decreased with the addition of 60 Mg ha?1 of manure from 62% to 52% in one of the soils studied and from 50% to 30% in the other. This amendment also reduced Zn proportion in water-soluble and exchangeable fractions from 17% to 13% in one of the soils. Manure decreased metal concentrations in shoots of A. halimus, from 97 to 35 mg kg?1 of Cu, from 211 to 98 mg kg?1 of Zn and from 1.4 to 0.6 mg kg?1 of Cd. In these treatments there was a higher plant growth due to the lower metal toxicity and the improvement of nutrients content in soil. This higher growth resulted in a higher total metal accumulation in plant biomass and therefore in a greater amount of metals removed from soil, so manure could be useful for phytoextraction purposes. This amendment increased metal accumulation in shoots from 37 to 138 mg pot?1 of Cu, from 299 to 445 mg pot?1 of Zn and from 1.8 to 3.7 mg pot?1 of Cd. Pine bark amendment did not significantly alter metal availability and its uptake by plants. Plants of A. halimus managed to reduce total Zn concentration in one of the soils from 146 to 130 mg kg?1, but its phytoextraction capacity was insufficient to remediate contaminated soils in the short-to-medium term. However, A. halimus could be, in combination with manure amendment, appropriate for the phytostabilization of metals in mine soils.

Bioaccessibility of heavy metals and risk assessment in urban gardens of Madrid

Human health problems and solutions. Urban gardening has spread worldwide in recent years as it enhances food security and selfsupply and promotes community integration. However urban soils are significantly enriched in trace elements relative to background levels. Exposure to the soil in urban gardens may therefore result in adverse health effects depending on the degree of contact during gardening, infant recreational activities and ingestion of vegetables grown in them. In order to evaluate this potential risk, 36 composite samples were collected from the top 20 cm of the soil of 6 urban gardens in Madrid. The aqua regia (pseudototal) and glycine-extractable (bioaccessible) concentrations of Co, Cr, Cu, Ni, Pb and Zn were determined by atomic absorption spectrophotometry. Additionally, pH, texture, Fe, Ca, and Mn concentrations, and organic matter and calcium carbonate contents were determined in all urban gardens and their influence on trace element bioaccessibility was analyzed.

Phytoextraction of heavy metals from mine soils using hyperaccumulator plants.

Phytoextraction is an environmental-friendly and cost-effective technology that uses metal hyperaccumulator plants to remove heavy metals from soils. The metals are absorbed by the roots, transported and accumulated in the aerial parts of the plants, which can be harvested and eliminated. The aim of this work was to study some hyperaccumulator species that could be useful to decontaminate mine soils and also to investigate the bioavailability and uptake of these metals by plants with the addition of organic amendments. Pot experiments were performed with soil samples collected from two mining areas in the north of Madrid, where there was an intense mining activity more than 50 years ago. Three species (Thlaspi arvense, Brassica juncea and Atriplex halimus) were grown under controlled conditions in pots filled with contaminated soils mixed with 0 Mg, 30 Mg and 60 Mg per hectare of two different organic amendments: a commercial compost made of pine bark, peat and wood fiber and other made of horse and sheep manure and wood fiber. Plants were harvested at the end of their crop cycle and were digested in order to measure metal concentration (Zn, Cu and Cd) in roots and shoots. Highest plant metal concentration was observed in pots treated with pine bark amendment and with pure soil due to an increase in metal bioavailability with decreasing pH. Also in those treatments the total plant biomass was lower, even some plants could not germinate. On the contrary, there was a lower metal concentration in plant tissues of pots with manure because its higher pH whereas plant growth was significantly larger so there was an incresing amount of metals removed from soil by plants. Comparing the three species results indicate a higher total metal uptake in A. halimus than B. juncea and T. arvense. In conclusion, results show that pH affects metal bioavailability and uptake by hyperaccumulator plants. Addition of organic amendments could be a successful technique for stabilization of metals in contaminated soils.

Phytoextraction of heavy metals from mine soils using hyperaccumulator plants

The aim of this work was to study some hyperaccumulator species that could be useful to decontaminate mine soils and also to investigate the bioavailability and uptake of these metals by plants with the addition of organic amendments. Pot experiments were performed with soil samples collected from two mining areas in the north of Madrid, where there was an intense mining activity more than 50 years ago. Three species (Thlaspi arvense, Brassica juncea and Atriplex halimus) were grown under controlled conditions in pots filled with contaminated soils mixed with 0 Mg, 30 Mg and 60 Mg per hectare of two different organic amendments: a commercial compost made of pine bark, peat and wood fiber and other made of horse and sheep manure and wood fiber. Plants were harvested at the end of their crop cycle and were digested in order to measure metal concentration (Zn, Cu and Cd) in roots and shoots. Highest plant metal concentration was observed in pots treated with pine bark amendment and with pure soil due to an increase in metal bioavailability with decreasing pH. Also in those treatments the total plant biomass was lower, even some plants could not germinate. On the contrary, there was a lower metal concentration in plant tissues of pots with manure because its higher pH whereas plant growth was significantly larger so there was an incresing amount of metals removed from soil by plants. Comparing the three species results indicate a higher total metal uptake in A. halimus than B. juncea and T. arvense. In conclusion, results show that pH affects metal bioavailability and uptake by hyperaccumulator plants. Addition of organic amendments could be a successful technique for stabilization of metals in contaminated soils.

Effects of soluble humic acids on the uptake of heavy metals by Vetiveria zizanioides (L.) Nash in contaminated mining soils

In the past, mining wastes were left wherever they might lie in the surroundings of the mine area. Unfortunately, inactive and abandoned mines continue to pollute our environment, reason why these sites should be restored with minimum impact. Phytoextraction is an environmental-friendly and cost-effective technology less harmful than traditional methods that uses metal hyperaccumulator or at least tolerant plants to extract heavy metals from polluted soils. One disadvantage of hyperaccumulator species is their slow growth rate and low biomass production. Vetiveria zizanioides (L.) Nash, perennial species adapted to Mediterranean climate has a strong root system which can reach up to 3 m deep, is fast growing, and can survive in sites with high metal levels (Chen et al., 2004). Due to the fact that metals in abandoned mine tailings become strongly bonded to soil solids, humic acids used as chelating agents could increase metal bioavailability (Evangelou et al., 2004; Wilde et al., 2005) and thereby promote higher accumulation in the harvestable parts of the plant. The objective of this study was to examine the performance of humic acid assisted phytoextraction using Vetiveria zizanioides (L.) Nash in heavy metals contaminated soils.

Emission factors from road dust resuspension in a Mediterranean freeway

Particulate matter emissions from paved roads are currently one of the main challenges for a sustainable transport in Europe. Emissions are scarcely estimated due to the lack of knowledge about the resuspension process severely hampering a reliable simulation of PM and heavy metals concentrations in large cities and evaluation of population exposure. In this study the Emission Factors from road dust resuspension on a Mediterranean freeway were estimated per single vehicle category and PM component (OC, EC, mineral dust and metals) by means of the deployment of vertical profiles of passive samplers and terminal concentration estimate. The estimated PM10 emission factors varied from 12 to 47 mg VKT?1 (VKT: Vehicle Kilometer Traveled) with an average value of 22.7 ? 14.2 mg VKT?1. Emission Factors for heavy and light duty vehicles, passenger cars and motorbikes were estimated, based on average fleet composition and EPA ratios, in 187e733 mg VKT?1, 33e131 VKT?1, 9.4e36.9 VKT?1 and 0.8e3.3 VKT?1, respectively. These range of values are lower than previous estimates in Mediterranean urban roads, probably due to the lower dust reservoir on freeways. PM emitted material was dominated by mineral dust (9e10 mg VKT?1), but also OC and EC were found to be major components and approximately 14 e25% and 2e9% of average PM exhaust emissions from diesel passenger cars on highways respectively.

Compostabilidad de envases de bolsas de PBAT+PLA y envases rígidos de PLA mediante tecnologías de pila y túnel

Los polímeros compostables suponen en torno al 30% de los bioplásticos destinados a envasado, siendo a su vez esta aplicación el principal destino de la producción de este tipo de materiales que, en el año 2013, superó 1,6 millones de toneladas. La presente tesis aborda la biodegradación de los residuos de envases domésticos compostables en medio aerobio para dos tipos de formato y materiales, envase rígido de PLA (Clase I) y dos tipos de bolsas de PBAT+PLA (Clases II y III). Sobre esta materia se han realizado diversos estudios en escala de laboratorio pero para otro tipo de envases y biopolímeros y bajo condiciones controladas del compost con alguna proyección particularizada en plantas. La presente tesis da un paso más e investiga el comportamiento real de los envases plásticos compostables en la práctica del compostaje en tecnologías de pila y túnel, tanto a escala piloto como industrial, dentro del procedimiento y con las condiciones ambientales de instalaciones concretas. Para ello, con el método seguido, se han analizado los requisitos básicos que debe cumplir un envase compostable, según la norma UNE – EN 13432, evaluando el porcentaje de biodegradación de los envases objeto de estudio, en función de la pérdida de peso seco tras el proceso de compostaje, y la calidad del compost obtenido, mediante análisis físico-químico y de fitotoxicidad para comprobar que los materiales de estudio no aportan toxicidad. En cuanto a los niveles de biodegrabilidad, los resultados permiten concluir que los envases de Clase I se compostan adecuadamente en ambas tecnologías y que no requieren de unas condiciones de proceso muy exigentes para alcanzar niveles de biodegradación del 100%. En relación a los envases de Clase II, se puede asumir que se trata de un material que se composta adecuadamente en pila y túnel industrial pero que requiere de condiciones exigentes para alcanzar niveles de biodegradación del 100% al afectarle de forma clara la ubicación de las muestras en la masa a compostar, especialmente en el caso de la tecnología de túnel. Mientras el 90% de las muestras alcanza el 100% de biodegradación en pila industrial, tan sólo el 50% lo consigue en la tecnología de túnel a la misma escala. En cuanto a los envases de Clase III, se puede afirmar que es un material que se composta adecuadamente en túnel industrial pero que requiere de condiciones de cierta exigencia para alcanzar niveles de biodegradación del 100% al poderle afectar la ubicación de las muestras en la masa a compostar. El 75% de las muestras ensayadas en túnel a escala industrial alcanzan el 100% de biodegradación y, aunque no se ha ensayado este tipo de envase en la tecnología de pila al no disponer de muestras, cabe pensar que los resultados de biodegrabilidad que hubiera podido alcanzar habrían sido, como mínimo, los obtenidos para los envases de Clase II, al tratarse de materiales muy similares en composición. Por último, se concluye que la tecnología de pila es más adecuada para conseguir niveles de biodegradación superiores en los envases tipo bolsa de PBAT+PLA. Los resultados obtenidos permiten también sacar en conclusión que, en el diseño de instalaciones de compostaje para el tratamiento de la fracción orgánica recogida selectivamente, sería conveniente realizar una recirculación del rechazo del afino del material compostado para aumentar la probabilidad de someter este tipo de materiales a las condiciones ambientales adecuadas. Si además se realiza un triturado del residuo a la entrada del proceso, también se aumentaría la superficie específica a entrar en contacto con la masa de materia orgánica y por tanto se favorecerían las condiciones de biodegradación. En cuanto a la calidad del compost obtenido en los ensayos, los resultados de los análisis físico – químicos y de fitotoxicidad revelan que los niveles de concentración de microorganismo patógenos y de metales pesados superan, en la práctica totalidad de las muestras, los niveles máximos permitidos en la legislación vigente aplicable a productos fertilizantes elaborados con residuos. Mediante el análisis de la composición de los envases ensayados se constata que la causa de esta contaminación reside en la materia orgánica utilizada para compostar en los ensayos, procedente del residuo de origen doméstico de la denominada “fracción resto”. Esta conclusión confirma la necesidad de realizar una recogida selectiva de la fracción orgánica en origen, existiendo estudios que evidencian la mejora de la calidad del residuo recogido en la denominada “fracción orgánica recogida selectivamente” (FORM). Compostable polymers are approximately 30% of bioplastics used for packaging, being this application, at same time, the main destination for the production of such materials exceeded 1.6 million tonnes in 2013. This thesis deals with the biodegradation of household packaging waste compostable in aerobic medium for two format types and materials, rigid container made of PLA (Class I) and two types of bags made of PBAT + PLA (Classes II and III). There are several studies developed about this issue at laboratory scale but for other kinds of packaging and biopolymers and under composting controlled conditions with some specifically plants projection. This thesis goes one step further and researches the real behaviour of compostable plastic packaging in the composting practice in pile and tunnel technologies, both at pilot and industrial scale, within the procedure and environmental conditions of concrete devices. Therefore, with a followed method, basic requirements fulfilment for compostable packaging have been analysed according to UNE-EN 13432 standard. It has been assessed the biodegradability percentage of the packaging studied, based on loss dry weight after the composting process, and the quality of the compost obtained, based on physical-chemical analysis to check no toxicity provided by the studied materials. Regarding biodegradability levels, results allow to conclude that Class I packaging are composted properly in both technologies and do not require high exigent process conditions for achieving 100% biodegradability levels. Related to Class II packaging, it can be assumed that it is a material that composts properly in pile and tunnel at industrial scale but requires exigent conditions for achieving 100% biodegradability levels for being clearly affected by sample location in the composting mass, especially in tunnel technology case. While 90% of the samples reach 100% of biodegradation in pile at industrial scale, only 50% achieve it in tunnel technology at the same scale. Regarding Class III packaging, it can be said that it is a material properly composted in tunnel at industrial scale but requires certain exigent conditions for reaching 100% biodegradation levels for being possibly affected by sample location in the composting mass. The 75% of the samples tested in tunnel at industrial scale reaches 100% biodegradation. Although this kind of packaging has not been tested on pile technology due to unavailability of samples, it is judged that biodegradability results that could be reached would have been, at least, the same obtained for Class II packaging, as they are very similar materials in composition. Finally, it is concluded that pile technology is more suitable for achieving highest biodegradation levels in bag packaging type of PBAT+PLA. Additionally, the obtained results conclude that, in the designing of composting devices for treatment of organic fraction selectively collected, it would be recommended a recirculation of the refining refuse of composted material in order to increase the probability of such materials to expose to proper environmental conditions. If the waste is grinded before entering the process, the specific surface in contact with organic material would also be increased and therefore biodegradation conditions would be more favourable. Regarding quality of the compost obtained in the tests, physical-chemical and phytotoxicity analysis results reveal that pathogen microorganism and heavy metals concentrations exceed, in most of the samples, the maximum allowed levels by current legislation for fertilizers obtained from wastes. Composition analysis of tested packaging verifies that the reason for this contamination is the organic material used for composting tests, comes from the household waste called “rest fraction”. This conclusion confirms the need of a selective collection of organic fraction in the origin, as existing studies show the quality improvement of the waste collected in the so-called “organic fraction selectively collected” (FORM).

Effects of sheep and horse manure and pine bark amendments on metal distribution and chemical properties of contaminated mine soils.

Mine soils usually contain large levels of heavy metals and poor fertility conditions which limit their reclamation and the application of phyto-remediation technologies. Two organic waste materials (pine bark compost and sheep and horse manure compost), with different pHs and varying degrees of humification and nutrient contents, were applied as amendments to assess their effects on copper (Cu) and zinc (Zn) bioavailability and on fertility conditions of mine soils. Soil samples collected from two abandoned mining areas near Madrid (Spain) were mixed with 0, 30 and 60 t ha?1 of the organic amendments. The concentrations of metals among the different mineral and organic fractions of soil were determined by several extraction procedures to study the metal distribution in the solid phase of the soil affected by the organic amendments. The results showed that the manure amendment increased the soil pH and the cation exchange capacity and enhanced the nutrient levels of these soils. The pine bark amendment decreased the soil pH and did not significantly change the nutrient status of soil. Soil pH, organic matter content and its degree of humification, which were altered by the amendments, were the main factors affecting Cu fractionation. Zn fractionation was mainly affected by soil pH. The addition of manure not only improved soil fertility, but also decreased metal bioavailability resulting in a reduction of metal toxicity. Conversely, pine bark amendment increased metal ioavailability. The use of sheep and horse manure could be a cost-effective practice for the restoration of contaminated mine soils.

Functional characterization of Rhizobium leguminosarum bv. viciae DmeRF, a cation diffusion facilitator system involved in nickel and cobalt resistance

In prokaryotes, nickel is an essential element participating in the structure of enzymes involved in multiple cellular processes. Nickel transport is a challenge for microorganisms since, although essential, high levels of this metal inside the cell are toxic. For this reason, bacteria have developed high-affinity nickel transporters as well as nickel-specific detoxification systems. Ultramafic soils, and soils contaminated with heavy metals are excellent sources of nickel resistant bacteria. Molecular analysis of strains isolated in the habitats has revealed novel genetic systems involved in adaptation to such hostile conditions.

Spatial and temporal variations of trace element distribution in soils and street dust of an industrial town in NW Spain: 15 years of study

Extensive spatial and temporal surveys, over 15 years, have been conducted in soil in urban parks and street dusts in one of the most polluted cities in western Europe, Avilés (NW Spain). The first survey was carried out in 1996, and since then monitoring has been undertaken every five years. Whilst the sampling site is a relatively small town, industrial activities (mainly the steel industry and Zn and Al metallurgy) and other less significant urban sources, such as traffic, strongly affect the load of heavy metals in the urban aerosol. Elemental tracers have been used to characterise the influence of these sources on the composition of soil and dust. Although PM10 has decreased over these years as a result of environmental measures undertaken in the city, some of the “industrial” elements still remain in concentrations of concern for example, up to 4.6% and 0.5% of Zn in dust and soil, respectively. Spatial trends in metals such as Zn and Cd clearly reflect sources from the processing industries. The concentrations of these elements across Europe have reduced over time, however the most recent results from Avilés revealed an upward trend in concentration for Zn, Cd, Hg and As. A risk assessment of the soil highlighted As as an element of concern since its cancer risk in adults was more than double the value above which regulatory agencies deem it to be unacceptable. If children were considered to be the receptors, then the risk nearly doubles from this element.

Composition, potential emissions and agricultural value of pig slurry from Spanish commercial farms

Pig slurry is a valuable fertilizer for crop production but at the same time its management may pose environmental risks. Slurry samples were collected from 77 commercial farms of four animal categories (gestating and lactating sows, nursery piglets and growing pigs) and analyzed for macronutrients, micronutrients, heavy metals and volatile fatty acids. Emissions of ammonia (NH3) and biochemical methane potential (BMP) were quantified. Slurry electrical conductivity, pH, dry matter content and ash content were also determined. Data analysis included an analysis of correlations among variables, the development of prediction models for gaseous emissions and the analysis of nutritional content of slurries for crop production. Descriptive information is provided in this work and shows a wide range of variability in all studied variables. Animal category affected some physicochemical parameters, probably as a consequence of different slurry management and use of cleaning water. Slurries from gestating sows and growing pigs tended to be more concentrated in nutrients, whereas the slurry from lactating sows and nursery piglets tended to be more diluted. Relevant relationships were found among slurry characteristics expressed in fresh basis and gas emissions. Predictive models using on-farm measurable parameters were obtained for NH3 (R2 = 0.51) and CH4