Anthropologic activities have transformed global biogeochemical cycling of heavy metals by emitting considerable quantities of these metals into the atmosphere from diverse sources. In spite of substantial and progressive developments in industrial processes and techniques to reduce environmental emissions, atmospheric contamination by toxic heavy metals and associated ecological and health risks are still newsworthy. Atmospheric heavy metals may be absorbed via foliar organs of plants after wet or dry deposition of atmospheric fallouts on plant canopy. Unlike root metal transfer, which has been largely studied, little is known about heavy metal uptake by plant leaves from the atmosphere. To the best of our understanding, significant research gaps exist regarding foliar heavy metal uptake. This is the first review regarding biogeochemical behaviour of heavy metals in atmosphere-plant system. The review summarizes the mechanisms involved in foliar heavy metal uptake, transfer, compartmentation, toxicity and in plant detoxification. We have described the biological and environmental factors that affect foliar uptake of heavy metals and compared the biogeochemical behaviour (uptake, translocation, compartmentation, toxicity and detoxification) of heavy metals for root and foliar uptake. The possible health risks associated with the consumption of heavy metal-laced food are also discussed.

Fine and ultrafine metallic particulate matters (PMs) are emitted from metallurgic activities in peri-urban zones into the atmosphere and can be deposited in terrestrial ecosystems. The foliar transfer of metals and metalloids and their fate in plant leaves remain unclear, although this way of penetration may be a major contributor to the transfer of metals into plants. This study focused on the foliar uptake of various metals and metalloids from enriched PM (Cu, Zn, Cd, Sn, Sb, As, and especially lead (Pb)) resulting from the emissions of a battery-recycling factory. Metal and metalloid foliar uptake by various vegetable species, exhibiting different morphologies, use (food or fodder) and life-cycle (lettuce, parsley and rye-grass) were studied. The mechanisms involved in foliar metal transfer from atmospheric particulate matter fallout, using lead (Pb) as a model element was also investigated. Several complementary techniques (micro-X-ray fluorescence, scanning electron microscopy coupled with energy dispersive X-ray microanalysis and time-of-flight secondary ion mass spectrometry) were used to investigate the localization and the speciation of lead in their edible parts, i.e. leaves. The results showed lead-enriched PM on the surface of plant leaves. Biogeochemical transformations occurred on the leaf surfaces with the formation of lead secondary species (PbCO(3) and organic Pb). Some compounds were internalized in their primary form (PbSO(4)) underneath an organic layer. Internalization through the cuticle or penetration through stomata openings are proposed as two major mechanisms involved in foliar uptake of particulate matter.

Throughout the world, urban agriculture supplies fresh local vegetables to city populations. However, the increasing anthropogenic uses of metal-containing nanoparticles (NPs) such as CuO-NPs in urban areas may contaminate vegetables through foliar uptake. This study focused on the CuO-NP transfer processes in leafy edible vegetables (i.e., lettuce and cabbage) to assess their potential phytotoxicity. Vegetables were exposed via leaves for 5, 10, or 15 days to various concentrations of CuO-NPs (0, 10, or 250 mg per plant). Biomass and gas exchange values were determined in relation to the Cu uptake rate, localization, and Cu speciation within the plant tissues. High foliar Cu uptake occurred after exposure for 15 days for lettuce [3773 mg (kg of dry weight)] and cabbage [4448 mg (kg of dry weight)], along with (i) decreased plant weight, net photosynthesis level, and water content and (ii) necrotic Cu-rich areas near deformed stomata containing CuO-NPs observed by scanning electron microscopy and energy dispersive X-ray microanalysis. Analysis of the CuO-NP transfer rate (7.8-242 μg day), translocation of Cu from leaves to roots and Cu speciation biotransformation in leaf tissues using electron paramagnetic resonance, suggests the involvement of plant Cu regulation processes. Finally, a potential health risk associated with consumption of vegetables contaminated with CuO-NPs was highlighted.

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At the global scale, high concentrations of particulate matter (PM) enriched with metal(loid)s are currently observed in the atmosphere of urban areas. Foliar lead uptake was demonstrated for vegetables exposed to airborne PM. Our main objective here was to highlight the health risk associated with the consumption of vegetables exposed to foliar deposits of PM enriched with the various metal(loid)s frequently observed in the atmosphere of urban areas (Cd, Sb, Zn and Pb). Leaves of mature cabbage and spinach were exposed to manufactured mono-metallic oxide particles (CdO, Sb2O3 and ZnO) or to complex process PM mainly enriched with lead. Total and bioaccessible metal(loid) concentrations were then measured for polluted vegetables and the various PM used as sources. Finally, scanning electronic microscopy coupled with energy dispersive X-ray microanalysis was used to study PM-phyllosphere interactions. High quantities of Cd, Sb, Zn and Pb were taken up by the plant leaves. These levels depended on both the plant species and nature of the PM, highlighting the interest of acquiring data for different plants and sources of exposure in order to better identify and manage health risks. A maximum of 2% of the leaf surfaces were covered with the PM. However, particles appeared to be enriched in stomatal openings, with up to 12% of their area occupied. Metal(loid) bioaccessibility was significantly higher for vegetables compared to PM sources, certainly due to chemical speciation changes. Taken together, these results confirm the importance of taking atmospheric PM into account when assessing the health risks associated with ingestion of vegetables grown in urban vegetable crops or kitchen gardens.

Ultrafine particulate matters enriched with metals are emitted into the atmosphere by industrial activities and can impact terrestrial and aquatic ecosystems. Thus, this study investigated the environmental effects of process particles from a lead-recycling facility after atmospheric deposition on soils and potential run-off to surface waters. The toxicity of lead-enriched PM for ecosystems was investigated on lettuce and bacteria by (i) germination tests, growth assays, lead transfer to plant tissues determination and (ii) Microtox analysis. The influence of ageing and soil properties on metal transfer and ecotoxicity was studied using three different soils and comparing various aged, spiked or historically long-term polluted soils. Finally, lead availability was assessed by 0.01 M CaCl(2) soil extraction. The results showed that process PM have a toxic effect on lettuce seedling growth and on Vibrio fischeri metabolism. Soil-PM interactions significantly influence PM ecotoxicity and bioavailability; the effect is complex and depends on the duration of ageing. Solubilisation or stabilisation processes with metal speciation changes could be involved. Finally, Microtox and phytotoxicity tests are sensitive and complementary tools for studying process PM ecotoxicity.

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Zirconium (Zr) is a transition metal that has both stable and radioactive isotopes.This metal has gained significant attention as a major pollutant of concern, partly because it has been prominent in the debate concerning the growing anthropogenic pressure on the environment. Its numerous past and present uses have induced significant soil and water pollution. Zr is generally considered to have low mobility in soils. The behavior of Zr particularly depends on the characteristics of the media in which it exists, and even its presence in the biosphere as a contaminate may affect its behavior. In this chapter, we describe the relationship between the behavior of Zrand its speciation in soils, its uptake and accumulation by plants, its translocation and toxicity inside plants, and mechanisms by which plants detoxify it.Zr is abundant and occurs naturally in the earth's crust. Zr emissions to the atmosphere are increasing from anthropogenic activities such as its use in industry and nuclear reactors. Zr forms various complexes with soil components, which reduces its soil mobility and phytoavailabilty. The mobility and phytoavailabilty of Zr in soil depend on its speciation and the physicochemical properties of soil that include soil pH, texture, and organic contents. Despite having low soil mobility and phytoavailability,amounts of Zr are absorbed by plants, mainly through the root system and can thereby enter the food chain.After plant uptake, Zr mainly accumulates in root cells. Zr does not have any known essential function in plant or animal metabolism. Although little published data are available, we conclude that the phytotoxicity of Zr is generally low.Notwithstanding, Zr can significantly reduce plant growth and can affect plantenzyme activity. When exposed to Zr-induced toxicity, plants possess numerous defense mechanisms to cope with the toxicity. Such strategies include Zr sequestration in plant roots and activation of various antioxidants. Because Zr may have impact on the biosphere, we believe it deserves to be evaluated in supplementary studies that will enhance the understanding of its behavior in soil-plant systems.