Uptake and translocation of inorganic and methylated arsenic species by plants

The uptake and translocation into shoots of arsenate, methylarsonate (MA), and dimethylarsinate (DMA) by 46 different plant species were studied. The plants (n = 3 per As species) were exposed for 24 h to 1 mg of As per litre under identical conditions. Total arsenic was measured in the roots and the shoots by acid digestion and inductively coupled plasma mass spectrometry from which, besides total As values, root absorption factors and shoot-to-root transfer factors were calculated. As uptake into the root for the different plant species ranged from 1.2 to 95 (mu g of As per g of dry weight) for As-V, from 0.9 to 44 for MA(V) and from 0.8 to 13 for DMA(V), whereas in shoots the As concentration ranged from 0.10 to 17 for As-V, 0.1 to 13 for MA(V), and 0.2 to 17 for DMA(V). The mean root absorption factor for As-V (1.2 to 95%) was five times higher than for DMA(V) (0.8 to 13%) and 2.5 times higher than for MA(V) (0.9 to 44%). Although the uptake of arsenic in the form of As-V was significantly higher than that of MA(V) and DMA(V), the translocation of the methylated species was more efficient in most plant species studied. Thus, an exposure of plants to DMA(V) or MA(V) can result in higher arsenic concentrations in the shoots than when exposed to As-V. Shoot-to-root transfer factors (TFs) for all plants varied with plant and arsenic species. While As-V had a median TF of 0.09, the TF of DMA(V) was nearly a factor of 10 higher (0.81). The median TF for MA(V) was in between (0.30). Although the TF for MA(V) correlates well with the TF for DMA(V), the plants can be separated into two groups according to their TF of DMA(V) in relation to their TF of As-V. One group can immobilise DMA(V) in the roots, while the other group translocates DMA(V) very efficiently into the shoot. The reason for this is as yet unknown.

Levels of cadmium and zinc in soil and plants following the toxic spill from a pyrite mine, Aznalcollar, Spain

On 25 April 1998, a breach of the tailings dam of the Los Frailes pyrite mine in southwestern Spain resulted in the release of 6 million m(3) of acidic water and toxic sludge high in heavy metals. Contaminated material extended 40 km downstream, affecting agricultural land and parts of the wildlife-rich Donana Natural and National Parks, including the Entremuros, a very important area for birds. We report on the concentrations, distributions and bioavailability of zinc and cadmium in soil and vegetation from the Entremuros in November 1998 and October 1999, following 2 'cleanup' operations. Levels of Zn and Cd in soil increased significantly over this period, although this was not reflected consistently in metal concentrations in emergent macrophytes. We recommend monitoring of further cleanup attempts in order to develop means of minimizing potential impacts to wildlife in the area.

Reproductive biomass in Holcus lanatus clones that differ in their phosphate uptake kinetics and mycorrhizal colonization

In normal populations of the common grass Holcus lanatus there is a polymorphism for arsenate resistance, manifested as suppressed phosphate uptake (SPU), and controlled by a major gene with dominant expression. A natural population of SPU plants had greater arbuscular-mycorrhizal colonization than wild type, nonSPU plants. It was hypothesized that, in order to survive alongside plants with a normal rate of phosphate (P) uptake, SPU plants would be more dependent on mycorrhizal associations. We performed an experiment using plants with SPU phenotypes from both arsenate mine spoils and uncontaminated soils, as well as plants with a nonSPU phenotype. They were grown with and without a mycorrhizal inoculum and added N, which altered plant P requirements. We showed that grasses with SPU phenotypes accumulated more shoot P than nonSPU plants, the opposite of the expected result. SPY plants also produced considerably more flower panicles, and had greater shoot and root biomass. The persistence of SPU phenotypes in normal populations is not necessarily related to mycorrhizal colonization as there were no differences in percentage AM colonization between the phenotypes. Being mycorrhizal reduced flower biomass production, as mycorrhizal SPU plants had lower shoot P concentrations and produced fewer flower panicles than non-mycorrhizal, nonSPU plants. We now hypothesize that the SPU phenotype is brought about by a genotype that results in increased accumulation of P in shoots, and that suppression of the rate of uptake is a consequence of this high shoot P concentration, operating by means of a homeostatic feedback mechanism. We also postulate that increased flower production is linked to a high shoot P concentration. SPU plants thus allocate more resources into seed production, leading to a higher frequency of SPU genes. Increased reproductive allocation reduces vegetative allocation and may affect competitive ability and hence survival, explaining the maintenance of the polymorphism. As mycorrhizal SPU plants behave more like nonSPU plants, AM colonization itself could play a major part in the maintenance of the SPU polymorphism.

Selenium in higher plants: understanding mechanisms for biofortification and phytoremediation:understanding mechanisms for biofortification and phytoremediation

Selenium (Se) is an essential micronutrient for many organisms, including plants, animals and humans. As plants are the main source of dietary Se, plant Se metabolism is therefore important for Se nutrition of humans and other animals. However, the concentration of Se in plant foods varies between areas, and too much Se can lead to toxicity. As we discuss here, plant Se uptake and metabolism can be exploited for the purposes of developing high-Se crop cultivars and for plant-mediated removal of excess Se from soil or water. Here, we review key developments in the current understanding of Se in higher plants. We also discuss recent advances in the genetic engineering of Se metabolism, particularly for biofortification and phytoremediation of Se-contaminated environments.

The molecular form of mercury in biota:identification of novel mercury peptide complexes in plants

The molecular structure of a variety of novel mercury-phytochelatin complexes was evidenced in rice plants exposed to inorganic mercury (Hg2+) using RP-HPLC with simultaneous detection via ICP-MS and ES-MS.

Arsenic uptake and metabolism in plants

Arsenic (As) is an element that is nonessential for and toxic to plants. Arsenic contamination in the environment occurs in many regions, and, depending on environmental factors, its accumulation in food crops may pose a health risk to humans.Recent progress in understanding the mechanisms of As uptake and metabolism in plants is reviewed here. Arsenate is taken up by phosphate transporters. A number of the aquaporin nodulin26-like intrinsic proteins (NIPs) are able to transport arsenite,the predominant form of As in reducing environments. In rice (Oryza sativa), arsenite uptake shares the highly efficient silicon (Si) pathway of entry to root cells and efflux towards the xylem. In root cells arsenate is rapidly reduced to arsenite, which is effluxed to the external medium, complexed by thiol peptides or translocated to shoots. One type of arsenate reductase has been identified, but its in planta functions remain to be investigated. Some fern species in the Pteridaceae family are able to hyperaccumulate As in above-ground tissues. Hyperaccumulation appears to involve enhanced arsenate uptake, decreased arsenite-thiol complexation and arsenite efflux to the external medium, greatly enhanced xylem translocation of arsenite, and vacuolar sequestration of arsenite in fronds. Current knowledge gaps and future research directions are also identified.

Can we trust mass spectrometry for determination of arsenic peptides in plants:comparison of LC-ICP-MS and LC-ES-MS/ICP-MS with XANES/EXAFS in analysis of Thunbergia alata

The weakest step in the analytical procedure for speciation analysis is extraction from a biological material into an aqueous solution which undergoes HPLC separation and then simultaneous online detection by elemental and molecular mass spectrometry (ICP-MS/ES-MS). This paper describes a study to determine the speciation of arsenic and, in particular, the arsenite phytochelatin complexes in the root from an ornamental garden plant Thunbergia alata exposed to 1 mg As L(-1) as arsenate. The approach of formic acid extraction followed by HPLC-ES-MS/ICP-MS identified different As(III)-PC complexes in the extract of this plant and made their quantification via sulfur (m/z 32) and arsenic (m/z 75) possible. Although sulfur sensitivity could be significantly increased when xenon was used as collision gas in ICP-qMS, or when HR-ICP-MS was used in medium resolution, the As:S ratio gave misleading results in the identification of As(III)-PC complexes due to the relatively low resolution of the chromatography system in relation to the variety of As-peptides in plants. Hence only the parallel use of ES-MS/ICP-MS was able to prove the occurrence of such arsenite phytochelatin complexes. Between 55 and 64% of the arsenic was bound to the sulfur of peptides mainly as As(III)(PC(2))(2), As(III)(PC(3)) and As(III)(PC(4)). XANES (X-ray absorption near-edge spectroscopy) measurement, using the freshly exposed plant root directly, confirmed that most of the arsenic is trivalent and binds to S of peptides (53% As-S) while 38% occurred as arsenite and only 9% unchanged as arsenate. EXAFS data confirmed that As-S and As-O bonds occur in the plants. This study confirms, for the first time, that As-peptides can be extracted by formic acid and chromatographically separated on a reversed-phase column without significant decomposition or de-novo synthesis during the extraction step.

Arsenic sequestration in iron plaque, its accumulation and speciation in mature rice plants (Oryza sativa L.)

A compartmented soil-glass bead culture system was used to investigate characteristics of iron plaque and arsenic accumulation and speciation in mature rice plants with different capacities of forming iron plaque on their roots. X-ray absorption near-edge structure spectra and extended X-ray absorption fine structure were utilized to identify the mineralogical characteristics of iron plaque and arsenic sequestration in plaque on the rice roots. Iron plaque was dominated by (oxyhydr)oxides, which were composed of ferrihydrite (81-100%), with a minor amount of goethite (19%) fitted in one of the samples. Sequential extraction and XANES data showed that arsenic in iron plaque was sequestered mainly with amorphous and crystalline iron (oxyhydr)oxides, and that arsenate was the predominant species. There was significant variation in iron plaque formation between genotypes, and the distribution of arsenic in different components of mature rice plants followed the following order: iron plaque > root > straw > husk > grain for all genotypes. Arsenic accumulation in grain differed significantly among genotypes. Inorganic arsenic and dimethylarsinic acid (DMA) were the main arsenic species in rice grain for six genotypes, and there were large genotypic differences in levels of DMA and inorganic arsenic in grain.