Speciation and lability of Ag-, AgCl-, and Ag2S-nanoparticles in soil determined by X-ray absorption spectroscopy and diffusive gradients in thin films.

Long-term speciation and lability of silver (Ag-), silver chloride (AgCl-), and silver sulfide nanoparticles (Ag2S-NPs) in soil were studied by X-ray absorption spectroscopy (XAS), and newly developed "nano" Diffusive Gradients in Thin Films (DGT) devices. These nano-DGT devices were designed specifically to avoid confounding effects when measuring element lability in the presence of nanoparticles. The aging profile and stabilities of the three nanoparticles and AgNO3 (ionic Ag) in soil were examined at three different soil pH values over a period of up to 7 months. Transformation of ionic Ag, Ag-NP and AgCl-NPs were dependent on pH. AgCl formation and persistence was observed under acidic conditions, whereas sulfur-bound forms of Ag dominated in neutral to alkaline soils. Ag2S-NPs were found to be very stable under all conditions tested and remained sulfur bound after 7 months of incubation. Ag lability was characteristically low in soils containing Ag2S-NPs. Other forms of Ag were linked to higher DGT-determined lability, and this varied as a function of aging and related speciation changes as determined by XAS. These results clearly indicate that Ag2S-NPs, which are the most environmentally relevant form of Ag that enter soils, are chemically stable and have profoundly low Ag lability over extended periods. This may minimize the long-term risks of Ag toxicity in the soil environment.

Agglomeration behaviour of titanium dioxide nanoparticles in river waters: A multi-method approach combining light scattering and field-flow fractionation techniques.

Titanium dioxide nanoparticles (TiO2 NPs) are currently one of the most prolifically used nanomaterials, resulting in an increasing likelihood of release to the environment. This is of concern as the potential toxicity of TiO2 NPs has been investigated in several recent studies. Research into their fate and behaviour once entering the environment is urgently needed to support risk assessment and policy development. In this study, we used a multi-method approach combining light scattering and field-flow fractionation techniques to assess both the aggregation behaviour and aggregate structure of TiO2 NPs in different river waters. Results showed that both the aggregate size and surface-adsorbed dissolved organic matter (DOM) were strongly related to the initial DOM concentration of the tested waters (i.e. R(2) > 0.90) suggesting that aggregation of TiO2 NPs is controlled by the presence and concentration of DOM. The conformation of the formed aggregates was also found to be strongly related to the surface-adsorbed DOM (i.e. R(2) > 0.95) with increasing surface-adsorbed DOM leading to more compact structures. Finally, the concentration of TiO2 NPs remaining in the supernatant after sedimentation of the larger aggregates was found to decrease proportionally with both increasing IS and decreasing DOM concentration, resulting in more than 95% sedimentation in the highest IS sample.

Measurement of inorganic arsenic species in rice after nitric acid extraction by HPLC-ICPMS: verification using XANES.

The measurement of As species in rice is normally accomplished by extraction followed by HPLC-ICPMS analysis. This method, however, has not been comprehensively validated by comparing these speciation results with XANES, which does not require sample extraction, due to the challenge of conducting XANES analysis at very low As concentrations. In this study As speciation data using nitric acid extraction/HPLC-ICPMS and XANES are compared to verify the efficacy of using 2% v/v nitric acid extraction and HPLC-ICPMS to measure inorganic As, DMA, and MA in reference rice materials and common rice varieties obtainable in Australia. Total As and As species (As(III), As(V), DMA, and MA) concentrations measured in 8 reference materials were in agreement with published values. XANES analysis was performed on 5 samples having total As concentrations ranging from 0.198 to 0.335 µg g(-1). XANES results gave similar proportions of total As(III), As(V), and DMA to HPLC-ICPMS. XANES was able to distinguish two forms of As(III): As(III) and As(III)GSH. Total As concentrations in rice samples varied from 0.006 to 0.45 µg g(-1) As (n = 47) with a mean ± std of 0.127 ± 0.112 µg g(-1) As with most As present as inorganic species (63 ± 26%). DMA was found in nearly all the rice samples with the majority of samples containing concentrations below 0.05 µg g(-1) As while MA concentrations were negligible (<0.003 µg g(-1) As). Six rice varieties produced in Australia, China, and Spain all had elevated DMA concentrations (0.170-0.399 µg g(-1) As) that were correlated with total As concentrations (r(2) = 0.7518). In conclusion, comparison of As speciation by HPLC-ICPMS and XANES showed that similar As species were detected indicating the appropriateness of using 2% v/v nitric acid for extraction of rice prior to speciation. Common rice varieties obtainable in Australia generally have low As concentrations with most As present as inorganic As.

Trends in hard X-ray fluorescence mapping: environmental applications in the age of fast detectors.

Environmental samples are extremely diverse but share a tendency for heterogeneity and complexity. This heterogeneity poses methodological challenges when investigating biogeochemical processes. In recent years, the development of analytical tools capable of probing element distribution and speciation at the microscale have allowed this challenge to be addressed. Of these available tools, laterally resolved synchrotron techniques such as X-ray fluorescence mapping are key methods for the in situ investigation of micronutrients and inorganic contaminants in environmental samples. This article demonstrates how recent advances in X-ray fluorescence detector technology are bringing new possibilities to environmental research. Fast detectors are helping to circumvent major issues such as X-ray beam damage of hydrated samples, as dwell times during scanning are reduced. They are also helping to reduce temporal beamtime requirements, making particularly time-consuming techniques such as micro X-ray fluorescence (µXRF) tomography increasingly feasible. This article focuses on µXRF mapping of nutrients and metalloids in environmental samples, and suggests that the current divide between mapping and speciation techniques will be increasingly blurred by the development of combined approaches.

Zinc from foliar-applied nanoparticle fertiliser is translocated to wheat grain: A 65Zn radiolabelled translocation study comparing conventional and novel foliar fertilisers.

Foliar zinc (Zn) fertilisers can be used to supplement or replace soil applications of Zn in situations where soil properties may decrease the plant bioavailability of Zn. However, conventional foliar Zn formulations such as zinc sulfate can cause leaf damage due to the rapid release of high amounts of Zn2+ into leaf tissue which can be locally phytotoxic. Zinc oxide nanoparticles (ZnO-NPs) offer an alternative approach by providing a more sustained release of Zn into leaf tissue, and potentially avoiding the need for multiple applications. We compared the efficacy of ZnO-NPs and microparticles (ZnO-MPs) to that of conventional formulations (ZnCl2 and ZnEDTA) in wheat. This is the first study to use 65Zn radiolabelled formulations and gamma spectrometry to determine the translocation of Zn to the grains and subsequent efficiency of foliar-applied ZnO-NP fertilisers. We found that ZnEDTA was the most efficient fertiliser in terms of the proportion of applied Zn translocated to wheat grain. We also investigated the effect of Zn application rate on fertiliser efficiency. For all forms of Zn, when plants were treated with Zn at 750 mg/L or 75 mg/L, there were no significant differences in the concentration of applied Zn translocated to the grain. This suggests that current Zn application rates could be decreased while still maintaining the nutritional quality of grain. Finally, using photo-stimulated luminescence (PSL) autoradiography and synchrotron-based X-ray fluorescence microscopy (XFM) we showed that the grain distribution of foliar-applied Zn mirrors that of Zn derived from root uptake.

Speciation and distribution of arsenic and localization of nutrients in rice grains.

Arsenic (As) contamination of rice grains and the generally low concentration of micronutrients in rice have been recognized as a major concern for human health. Here, we investigated the speciation and localization of As and the distribution of (micro)nutrients in rice grains because these are key factors controlling bioavailability of nutrients and contaminants. Bulk total and speciation analyses using high-pressure liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) and X-ray absorption near-edge spectroscopy (XANES) was complemented by spatially resolved microspectroscopic techniques (micro-XANES, micro-X-ray fluorescence (micro-XRF) and particle induced X-ray emission (PIXE)) to investigate both speciation and distribution of As and localization of nutrients in situ. The distribution of As and micronutrients varied between the various parts of the grains (husk, bran and endosperm) and was characterized by element-specific distribution patterns. The speciation of As in bran and endosperm was dominated by As(III)-thiol complexes. The results indicate that the translocation from the maternal to filial tissues may be a bottleneck for As accumulation in the grain. Strong similarities between the distribution of iron (Fe), manganese (Mn) and phosphorus (P) and between zinc (Zn) and sulphur (S) may be indicative of complexation mechanisms in rice grains.

Field evaluation of Cd and Zn phytoextraction potential by the hyperaccumulators Thlaspi caerulescens and Arabidopsis halleri.

Field trials were undertaken to investigate the effect of the application of metal mobilizing agents, different sowing strategies and length of growing season on the extraction of Cd and Zn from soils by Thlaspi caerulescens and Arabidopsis halleri. None of the mobilizing agents used enhanced metal accumulation by T. caerulescens. Between 1998 and 2000, on average across plots where Cd or Zn exceeded allowable limits, T. caerulescens removed 1.3 and 0.3% of the total soil Cd and Zn. In one season when T. caerulescens was grown for 14 months, 21.7 and 4.4% of the total soil Cd and Zn was removed. This was larger than values found when T. caerulescens was grown for 4 months. A. halleri accumulated similar concentrations of Zn, but lower Cd concentrations than T. caerulescens. The results indicate that metal phytoextraction using T. caerulescens can be used to clean up soils moderately contaminated by Cd.

Evaluating the mobility of polymer-stabilised zero-valent iron nanoparticles and their potential to co-transport contaminants in intact soil cores.

The use of zero-valent iron nanoparticles (nZVI) has been advocated for the remediation of both soils and groundwater. A key parameter affecting nZVI remediation efficacy is the mobility of the particles as this influences the reaction zone where remediation can occur. However, by engineering nZVI particles with increased stability and mobility we may also inadvertently facilitate nZVI-mediated contaminant transport away from the zone of treatment. Previous nZVI mobility studies have often been limited to model systems as the presence of background Fe makes detection and tracking of nZVI in real systems difficult. We overcame this problem by synthesising Fe-59 radiolabelled nZVI. This enabled us to detect and quantify the leaching of nZVI-derived Fe-59 in intact soil cores, including a soil contaminated by Chromated-Copper-Arsenate. Mobility of a commercially available nZVI was also tested. The results showed limited mobility of both nanomaterials; <1% of the injected mass was eluted from the columns and most of the radiolabelled nZVI remained in the surface soil layers (the primary treatment zone in this contaminated soil). Nevertheless, the observed breakthrough of contaminants and nZVI occurred simultaneously, indicating that although the quantity transported was low in this case, nZVI does have the potential to co-transport contaminants. These results show that direct injection of nZVI into the surface layers of contaminated soils may be a viable remediation option for soils such as this one, in which the mobility of nZVI below the injection/remediation zone was very limited. This Fe-59 experimental approach can be further extended to test nZVI transport in a wider range of contaminated soil types and textures and using different application methods and rates. The resulting database could then be used to develop and validate modelling of nZVI-facilitated contaminant transport on an individual soil basis suitable for site specific risk assessment prior to nZVI remediation.

Analytical characterisation of nanoscale zero-valent iron: A methodological review.

Zero-valent iron nanoparticles (nZVI) have been widely tested as they are showing significant promise for environmental remediation. However, many recent studies have demonstrated that their mobility and reactivity in subsurface environments are significantly affected by their tendency to aggregate. Both the mobility and reactivity of nZVI mainly depends on properties such as particle size, surface chemistry and bulk composition. In order to ensure efficient remediation, it is crucial to accurately assess and understand the implications of these properties before deploying these materials into contaminated environments. Many analytical techniques are now available to determine these parameters and this paper provides a critical review of their usefulness and limitations for nZVI characterisation. These analytical techniques include microscopy and light scattering techniques for the determination of particle size, size distribution and aggregation state, and X-ray techniques for the characterisation of surface chemistry and bulk composition. Example characterisation data derived from commercial nZVI materials is used to further illustrate method strengths and limitations. Finally, some important challenges with respect to the characterisation of nZVI in groundwater samples are discussed.

Non-labile silver species in biosolids remain stable throughout 50 years of weathering and ageing.

Increasing commercial use of nanosilver has focussed attention on the fate of silver (Ag) in the wastewater release pathway. This paper reports the speciation and lability of Ag in archived, stockpiled, and contemporary biosolids from the UK, USA and Australia, and indicates that biosolids Ag concentrations have decreased significantly over recent decades. XANES revealed the importance of reduced-sulfur binding environments for Ag speciation in materials ranging from freshly produced sludge to biosolids weathered under ambient environmental conditions for more than 50 years. Isotopic dilution with (110 m)Ag showed that Ag was predominantly non-labile in both fresh and aged biosolids (13.7% mean lability), with E-values ranging from 0.3 to 60 mg/kg and 5 mM CaNO3 extractable Ag from 1.2 to 609 µg/kg (0.002-3.4% of the total Ag). This study indicates that at the time of soil application, biosolids Ag will be predominantly Ag-sulfides and characterised by low isotopic lability.

Aggregation behaviour of engineered nanoparticles in natural waters: characterising aggregate structure using on-line laser light scattering.

Adsorption of natural organic matter, aggregation and disaggregation have been identified as three of the main processes affecting the fate and behaviour of engineered nanoparticles (ENPs) in aquatic environments. However, although several methods have been developed to study the aggregation behaviour of ENPs in natural waters, there are only a few studies focusing on the fate of such aggregates and their potential disaggregation behaviour. In this study, we proposed and demonstrated a simple method for characterising the aggregation behaviour and aggregate structure of ENPs in different natural waters. Both the aggregate size of ENPs and their adsorption capacity for dissolved organic matter (DOM) were strongly related (R(2)>0.97, p<.05) to the combined effect of initial concentration of dissolved organic matter (DOM) and the ionic strength of the natural waters. The structure of the formed aggregates was strongly correlated (R(2)>0.95, p<.05) to the amount of DOM adsorbed by the ENPs during the aggregation process. Under high ionic strength conditions, aggregation is mainly governed by diffusion and the aggregates formed under these conditions showed the lowest stability and fractal dimension, forming linear, chain-like aggregates. In contrast, under low ionic strength conditions, the aggregate structure was more compact, most likely due to strong chemical binding with DOM and bridging mechanisms involving divalent cations formed during reaction-limited aggregation.

Physiological evidence for a high-affinity cadmium transporter highly expressed in a Thlaspi caerulescens ecotype.

• Uptake kinetics and translocation characteristics of cadmium and zinc are presented for two contrasting ecotypes of the Cd/Zn hyperaccumulator Thlaspi caerulescens, Ganges (southern France) and Prayon (Belgium). • Experiments using radioactive isotopes were designed to investigate the physiology of Cd and Zn uptake, and a pressure-chamber system was employed to collect xylem sap. • In contrast to similar Zn uptake and translocation, measurements of concentration-dependent influx of Cd revealed marked differences between ecotypes. Ganges alone showed a clear saturable component in the low Cd concentration range; maximum influx Vmax for Cd was fivefold higher in Ganges; and there was a fivefold difference in the Cd concentration in xylem sap. Addition of Zn to the uptake solution at equimolar concentration to Cd did not decrease Cd uptake by Ganges, but caused a 35% decrease in Prayon. • There is strong physiological evidence for a high-affinity, highly expressed Cd transporter in the root cell plasma membranes of the Ganges ecotype of T. caerulescens. This raises evolutionary questions about specific transporters for non-essential metals. The results also show the considerable scope for selecting hyperaccumulator ecotypes to achieve higher phytoextraction efficiencies.

Heavy metal content and mutagenic activity, evaluated by Vicia faba micronucleus test, of Tiber river sediments.

Tiber river sediment samples, collected in October 1995, were tested for mutagenicity by the micronucleus test in Vicia faba root tips. Four stations were studied within the urban area of Rome: (1) Castel Giubileo, at the entry of the urban area; (2) Ponte Tor di Quinto, immediately after the confluence of the tributary river Aniene; (3) Ponte Sublicio, in the middle of the city; and (4) Ponte della Magliana, immediately outside Rome, 20 km from the sea. Since no significant increase in micronucleus frequency was observed in any of the tested stations compared to control (while in previous campaigns mutagenic activity was observed in some of the same stations), it can be assumed an interesting recovery from mutagenic pollution in the 2 last years. The samples were analysed for pH value, nitrogen, organic matter and carbonate content, and the concentration of some potentially mutagenic heavy metal ions (Zn, Cd, Ni, V, Cu) was assessed. In all samples, a concentration of heavy metals higher than unpolluted areas was observed. However, the alkaline pH measured should keep them as non-bioavailable elements.

Foliar and soil uptake of 134Cs and 85Sr by grape vines.

The foliar and soil uptake of 134Cs and 85Sr by grape vines and their subsequent translocation to fruits and to the other plant compartments is described. Grape vine plants growing in pots and kept in an open field were contaminated with 134Cs and 85Sr in ionic form by sprinkling on the aerial part, or by addition to the soil. Sprinkling was effected at the stage of ripening of the grapes. Interception, determined by analysing all the leaves picked from three plants after the sprinkling, was approx. 50% of the sprayed activity. Soil contamination was effected after the fruit setting, 1 month earlier than sprinkling. At ripening, the whole plant was picked. Berries, leaves, shoots, stems, roots and soil were analysed by gamma spectrometry. Activities of the different parts of the plant were expressed as: (a) translocation factors of intercepted activity for foliar treatment; (b) transfer factors of activity applied to the soil for soil treatment. Both factors were calculated per unit of fresh weight, or referred to the total biomass of the plant compartment. Leaf-to-fruit translocation factors per unit of weight are of the order of magnitude of 10(-1) for 134Cs and of 10(-2) for 85Sr. One/two order of magnitude lower are soil-to-fruit transfer factors: 10(-3) both for 134Cs and for 85Sr. Radiocesium behaves quite differently from radiostrontium, but the behaviour of both radionuclides within the grape vine is independent of the path of absorption, by leaves or by roots. 134Cs is absorbed more easily than 85Sr by plant foliage, but is absorbed with more difficulty than 85Sr by roots. After absorption by either route, radiocesium concentrates mainly in the fruit compartment of the plant, whereas radiostrontium concentrates in the foliar compartment. Loss from the aerial part of the plant is higher for 85Sr than for 134Cs. 85Sr remains more available in soil than 134Cs, is more absorbed by roots and is more leached downward. After foliar contamination, the dominant pathway of radionuclides to reach the soil is by dislodging of non-absorbed radionuclides or senescent cells from the aerial part of the plant by action of wind and rain.

Leaching of heavy metals from contaminated soils using EDTA.

Ethylenediaminetetraacetic acid (EDTA) extraction of Zn, Cd, Cu and Pb from four contaminated soils was studied using batch and column leaching experiments. In the batch experiment, the heavy metals extracted were virtually all as 1:1 metal-EDTA complexes. The ratios of Zn, Cd, Cu and Pb of the extracted were similar to those in the soils, suggesting that EDTA extracted the four heavy metals with similar efficiency. In contrast, different elution patterns were obtained for Zn, Cd, Cu and Pb in the column leaching experiment using 0.01 M EDTA. Cu was either the most mobile or among the most mobile of the four heavy metals, and its peak concentration corresponded with the arrival of full strength EDTA in the leachate. The mobility of Zn and Cd was usually slightly lower than that of Cu. Pb was the least mobile, and its elution increased after the peaks of Cu and Zn. Sequential fractionations of leached and un-leached soils showed that heavy metals in various operationally defined fractions contributed to the removal by EDTA. Considerable mobilisation of Fe occurred in two of the four soils during EDTA leaching. Decreases in the Fe and Mn oxide fraction of heavy metals after EDTA leaching occurred in both soils, as well as in a third soil that showed little Fe mobilisation. The results suggest that the lability of metals in soil, the kinetics of metal desorption/dissolution and the mode of EDTA addition were the main factors controlling the behaviour of metal leaching with EDTA.

Phytoremediation of heavy metal-contaminated soils: natural hyperaccumulation versus chemically enhanced phytoextraction.

A pot experiment was conducted to compare two strategies of phytoremediation: natural phytoextraction using the Zn and Cd hyperaccumulator Thlaspi caerulescens J. Presl & C. Presl versus chemically enhanced phytoextraction using maize (Zea mays L.) treated with ethylenediaminetetraacetic acid (EDTA). The study used an industrially contaminated soil and an agricultural soil contaminated with metals from sewage sludge. Three crops of T. caerulescens grown over 391 d removed more than 8 mg kg(-1) Cd and 200 mg kg(-1) Zn from the industrially contaminated soil, representing 43 and 7% of the two metals in the soil. In contrast, the high concentration of Cu in the agricultural soil severely reduced the growth of T. caerulescens, thus limiting its phytoextraction potential. The EDTA treatment greatly increased the solubility of heavy metals in both soils, but this did not result in a large increase in metal concentrations in the maize shoots. Phytoextraction of Cd and Zn by maize + EDTA was much smaller than that by T. caerulescens from the industrially contaminated soil, and was either smaller (Cd) or similar (Zn) from the agricultural soil. After EDTA treatment, soluble heavy metals in soil pore water occurred mainly as metal-EDTA complexes, which were persistent for several weeks. High concentrations of heavy metals in soil pore water after EDTA treatment could pose an environmental risk in the form of ground water contamination.

A multi-technique investigation of copper and zinc distribution, speciation and potential bioavailability in biosolids.

The use of biosolids in agriculture continues to be debated, largely in relation to their metal contents. Our knowledge regarding the speciation and bioavailability of biosolids metals is still far from complete. In this study, a multi-technique approach was used to investigate copper and zinc speciation and partitioning in one contemporary and two historical biosolids used extensively in previous research and field trials. Using wet chemistry and synchrotron spectroscopy techniques it was shown that copper/zinc speciation in the biosolids was largely equivalent despite the biosolids being derived from different countries over a 50 year period. Furthermore, copper speciation was consistently dominated by sorption to organic matter whereas Zn partitioned mainly to iron oxides. These data suggest that the results of historical field trials are still relevant for modern biosolids and that further risk assessment studies should concentrate particularly on Cu as this metal is associated with the mineralisable biosolids fraction.

Effect of water treatment residuals on soil phosphorus, copper and aluminium availability and toxicity.

Water treatment residuals (WTRs) are produced by the treatment of potable water with coagulating agents. Beneficial recycling in agriculture is hampered by the fact that WTRs contain potentially toxic contaminants (e.g. copper and aluminium) and they bind phosphorus strongly. These issues were investigated using a plant bioassay (Lactuca sativa), chemical extractions and an isotopic dilution technique. Two WTRs were applied to an acidic and a neutral pH soil at six rates. Reductions in plant growth in amended soils were due to WTR-induced P deficiency, rather than Al or Cu toxicity. The release of potentially toxic Al from WTRs was found to be mitigated by their alkaline nature and pH buffering capacity. However, acidification of WTRs was shown to release more soluble Al than soil naturally high in Al. Copper availability was relatively low in all treatments. However, the lability of WTR-Cu increased when the WTR was applied to the soil.

Cellular compartmentation of cadmium and zinc in relation to other elements in the hyperaccumulator Arabidopsis halleri.

The cellular compartmentation of elements was analysed in the Zn hyperaccumulator Arabidopsis halleri (L.) O'Kane & Al-Shehbaz (=Cardaminopsis halleri) using energy-dispersive X-ray microanalysis of frozen-hydrated tissues. Quantitative data were obtained using oxygen as an internal standard in the analyses of vacuoles, whereas a peak/background ratio method was used for quantification of elements in pollen and dehydrated trichomes. Arabidopsis halleri was found to hyperaccumulate not only Zn but also Cd in the shoot biomass. While large concentrations of Zn and Cd were found in the leaves and roots, flowers contained very little. In roots grown hydroponically, Zn and Cd accumulated in the cell wall of the rhizodermis (root epidermis), mainly due to precipitation of Zn/Cd phosphates. In leaves, the trichomes had by far the largest concentrations of Zn and Cd. Inside the trichomes there was a striking sub-cellular compartmentation, with almost all the Zn and Cd being accumulated in a narrow ring in the trichome base. This distribution pattern was very different from that for Ca and P. The epidermal cells other than trichomes were very small and contained lower concentrations of Zn and Cd than mesophyll cells. In particular, the concentrations of Cd and Zn in the mesophyll cells increased markedly in response to increasing Zn and Cd concentrations in the nutrient solution. This indicates that the mesophyll cells in the leaves of A. halleri are the major storage site for Zn and Cd, and play an important role in their hyperaccumulation.