Silver nanoparticles: behaviour and effects in the aquatic environment

This review summarises and evaluates the present knowledge on the behaviour, the biological effects and the routes of uptake of silver nanoparticles (Ag NPs) to organisms, with considerations on the nanoparticle physicochemistry in the ecotoxicity testing systems used. Different types of Ag NP syntheses, characterisation techniques and predicted current and future concentrations in the environment are also outlined. Rapid progress in this area has been made over the last few years, but there is still a critical lack of understanding of the need for characterisation and synthesis in environmental and ecotoxicological studies. Concentration and form of nanomaterials in the environment are difficult to quantify and methodological progress is needed, although sophisticated exposure models show that predicted environmental concentrations (PECs) for Ag NPs in different environmental compartments are at the range of ng L(-1) to mg kg(-1). The ecotoxicological literature shows that concentrations of Ag NPs below the current and future PECs, as low as just a few ng L(-1), can affect prokaryotes, invertebrates and fish indicating a significant potential, though poorly characterised, risk to the environment. Mechanisms of toxicity are still poorly understood although it seems clear that in some cases nanoscale specific properties may cause biouptake and toxicity over and above that caused by the dissolved Ag ion. This review concludes with a set of recommendations for the advancement of understanding of the role of nanoscale silver in environmental and ecotoxicological research.     

Factors affecting metal toxicity to (and accumulation by) aquatic organisms — Overview

This literature review encompasses aquatic environmental toxicities of metals and metalloids. The emphasis is on the influencing factors on metal toxicity to aquatic organisms. The effects of environmental factors on metal uptake are also discussed. The factors can be divided into biotic and abiotic. The biotic factors include tolerance, size and life stages, species, and nutrition related to the test organisms. The abiotic factors include organic substances, pH, temperature, alkalinity and hardness, inorganic ligands, interactions, sediments, and others. These factors can alter metal toxicity in the aquatic environment substantially, mostly causing attenuating effect. The literature shows divergent results. For example, the interactions between Cd and Zn were reported to be synergistic by some researchers and antagonistic by others. It is recommended that environmental hazard assessment takes into consideration the results of standard toxicity tests and site-specific conditions which can moderate metal toxicity considerably.     

Environmental risk assessment of metals: tools for incorporating bioavailability

In this paper, some of the main processes and parameters which affect metal bioavailability and toxicity in the aquatic environment and its implications for metal risk assessment procedures will be discussed. It has become clear that, besides chemical processes (speciation, complexation), attention should also be given to physiological aspects for predicting metal toxicity. The development of biotic ligand models (BLMs), which combine speciation models with more biologically oriented models (e.g. GSIM), has offered an answer to this need. The various BLMs which have been developed and/or refined for a number of metals (e.g. Cu, Ag, Zn) and species (algae, crustaceans, fish) are discussed here. Finally, the potential of the BLM approach is illustrated through a theoretical exercise in which chronic zinc toxicity to Daphnia magna is predicted in three regions, taking the physico-chemical characteristics of these areas into account.     

Determining sediment quality for regulatory proposes using fish chronic bioassays

Sediment quality assessments for regulatory purposes (i.e. dredged material disposal) are characterized by linking chemical and acute ecotoxicological data. The design of chronic bioassays that incorporate more sensible endpoints than acute tests is discussed to address sediment quality for environmental quality assessment and regulatory proposes. The chronic tests use juveniles of commercial species of fish Sparus aurata and Solea senegalensis, to assess sediment toxicity in samples collected along different littoral areas in the North and the South of Spain. The organisms were exposed during 60 days and sublethal endpoints were selected including biomarkers of exposure to metals (metallothioneins - MTs) and to organic contaminants (ethoxyresorufin-O-deethylase activity - EROD activity) and biomarkers of effect (histopathology in different tissues, gill and liver). A Multivariate Analysis Approach was conducted in order to associate these biological responses with sediment metal concentration from the ports and with chemical residues in biological tissues exposed to sediments under laboratory conditions.     

Toxicity of zinc oxide nanoparticles in the earthworm, Eisenia fetida and subcellular fractionation of Zn

The extensive use of nanoparticles (NPs) in a variety of applications has raised great concerns about their environmental fate and biological effects. This study examined the impact of dissolved organic matter (DOM) and salts on ZnO NP dispersion/solubility and toxicity to the earthworm Eisenia fetida. To be able to better evaluate the toxicity of NPs, exposure in agar and on filter paper was proposed for enabling a comparison of the importance of different uptake routes. A dose-related increase in mortality was observed in earthworms exposed in agar with almost 100% mortality after 96 h exposure to the highest concentration (1000 mg ZnO/kg agar). Scanning electron microscopy (SEM) showed that the addition of salts enhanced the aggregation of ZnO NPs in agar and consequently affected the dissolution behavior and biological availability of the particles. On filter paper, mortality was the highest at the lowest exposure concentration (50 mg ZnO/L) and seemed to decrease with increasing exposure levels. TEM images of ZnO showed that the solubility and morphology of NPs were changed dramatically upon the addition of humic acids (HA). The subcellular distribution pattern of Zn in earthworms after 96 h exposure in agar and on filter paper showed that the Zn taken up via dietary ZnO particles (from agar) was mainly found in organelles and the cytosol while the Zn accumulated as soluble Zn from filter paper was mainly distributed in cell membranes and tissues. Antioxidant enzymatic activities (SOD, CAT, and GSH-px) were investigated in the worms surviving the toxicity tests. A slight increase of SOD activities was observed at the lowest exposure dose of ZnO (50mg/kg), followed by a decrease at 100mg/kg in the agar cubes. Activities of both CAT and GSH-Px enzymes were not significantly influenced in the worms exposed to agar, although a slight decrease at 500 and 1000 mg ZnO/kg agar was observed. A similar change trend of SOD activities was observed for the earthworms on filter paper, but a significant decrease began at a higher ZnO NP concentration of 500 mg ZnO/L. The use of soil extracts instead of deionized water (DW) to simulate a realistic exposure system significantly reduced the toxicity of the ZnO NPs on filter paper, which increases the predictive power of filter paper toxicity tests for the environmental risk assessment of NPs.     

Characterisation of heavy metal discharge into the Ria of Huelva

The Ria of Huelva estuary, in SW Spain, is known to be one of the most heavy metal contaminated estuaries in the world. River contribution to the estuary of dissolved Cu, Zn, Mn, Cr, Ni, Cd, and As were analysed for the period 1988-2001. The obtained mean values show that this contribution, both because of the magnitude of total metals (895.1 kg/h), composition, toxicity (8.7 kg/h of As+Cd+Pb) and persistence, is an incomparable case in heavy metal contamination of estuaries. The amount and typology of heavy metal discharge to the Ria of Huelva are related to freshwater flow (and, consequently, to rainfall); as a result, two different types of heavy metal discharge can be distinguished in the estuary: during low water (50% of the days), with only 19.3 kg/h of heavy metals, and during high water or flood (17% of the days), where daily maximum discharge of 72,475 kg of heavy metals were recorded, from which 1481 kg were of As, 470 kg of Pb, and 170 kg of Cd. In the most frequent situation (77% of the days), the Odiel River discharges from 90% to 100% of the freshwater received by the estuary. Despite this, the high concentration of heavy metals in the Tinto River water causes this river to discharge into the Ria of Huelva 12.5% of fluvial total dissolved metal load received by the estuary.     

Effects of dissolved organic matter on toxicity and bioavailability of copper for lettuce sprouts

It is well known that dissolved organic matter in soil solution may affect the toxicity or bioavailability of heavy metals to plants, but existing information on various organic substances is insufficient for treating problems with heavy metal-contaminated soils. To clarify how dissolved organic matter alters the toxicity and bioavailability of metals, we germinated lettuce seeds exposed to solutions containing Cu and several kinds of dissolved organic matters. Low molecular weight organic acids (citric, malic, and oxalic acids) increased the toxicity and bioavailability of Cu, but low concentrations of the synthetic chelators ethylenediamine tetra-acetic acid (EDTA) and diethylenetriamine penta-acetic acid (DTPA) decreased the toxicity and bioavailability of Cu. In contrast, humic acid appeared to be the most effective organic substance for detoxifying Cu, even though it did not significantly decrease the bioavailability of Cu. Consequently, the bioavailability and toxic effects of Cu in soil depend on the nature of coexisting organic substances in the soil solution.     

Trace metal bioaccumulation: models, metabolic availability and toxicity

Aquatic invertebrates take up and accumulate trace metals whether essential or non-essential, all of which have the potential to cause toxic effects. Subsequent tissue and body concentrations of accumulated trace metals show enormous variability across metals and invertebrate taxa. Accumulated metal concentrations are interpreted in terms of different trace metal accumulation patterns, dividing accumulated metals into two components - metabolically available metal and stored detoxified metal. Examples of different accumulation patterns are described from crustaceans but have a general applicability to all aquatic invertebrates. Toxicity does not depend on total accumulated metal concentration but is related to a threshold concentration of internal metabolically available metal. Toxicity ensues when the rate of metal uptake from all sources exceeds the combined rates of detoxification and excretion (if present) of the metal concerned. The biodynamic model of trace metal bioaccumulation allows the prediction and explanation of widely differing accumulated trace metal concentrations in organisms, combining geochemical analyses of environmental metal concentrations with the measurement of key physiological parameters for a species from the site under consideration. The combination of the biodynamic model as a unified explanation of metal bioaccumulation with an understanding of the relationship between accumulation and toxicity sets the stage for a realistic understanding of the significance of trace metal concentrations in aquatic invertebrates.     

Metal uptake, transport and release by wetland plants: implications for phytoremediation and restoration

Marshes have been proposed as sites for phytoremediation of metals. The fate of metals within plant tissues is a critical issue for effectiveness of this process. In this paper we review studies that investigate the effects of plants on metals in wetlands. While most of these marsh plant species are similar in metal uptake patterns and in concentrating metals primarily in roots, some species retain more of their metal burden in below ground structures than other species, which redistribute a greater proportion of metals into above ground tissues, especially leaves. Storage in roots is most beneficial for phytostabilization of the metal contaminants, which are least available when concentrated below ground. Plants may alter the speciation of metals and may also suffer toxic effects as a result of accumulating them. Metals in leaves may be excreted through salt glands and thereby returned to the marsh environment. Metal concentrations of leaf and stem litter may become enriched in metals over time, due in part to cation adsorption or to incorporation of fine particles with adsorbed metals. Several studies suggest that metals in litter are available to deposit feeders and, thus, can enter estuarine food webs. Marshes, therefore, can be sources and well as sinks for metal contaminants. Phragmites australis, an invasive species in the northeast U.S. sequesters more metals below ground than the native Spartina alterniflora, which also releases more via leaf excretion. This information is important for the siting and use of wetlands for phytoremediation as well as for marsh restoration efforts.     

Fractionation studies and bioaccumulation of sediment-bound heavy metals in Kolleru lake by edible fish

Kolleru lake is the largest fresh water lake in the districts of East and West Godavari of Andhra Pradesh, India. Many anthropogenic sources contribute to the heavy metal pollution in the lake and the bioaccumulation of heavy metals in fish helps in assessing the aquatic pollution. Total contents and fractionation of selected heavy metals, viz., Zn, Cu, Cd, Pb, Cr, Ni and Co were measured in sediment sample and three edible fish. The investigation aimed at revealing differences in the accumulation pattern of heavy metals in fish inhabiting sediments characterized by varying metal bioavailability. The metal concentrations were found to be greater than the background concentrations of sediments indicating the anthropogenic origin of metals. Good recovery values were obtained for metal contents in sediments and fish. Large fractions of Zn, Cd and Cu were associated with mobile fraction of sediment and showed greater bioaccumulation in fish whereas Ni and Co were least mobilisable. The results clearly indicate that the fish of Kolleru lake are contaminated with metals and not advisable for human consumption.     

Speciation and hydrological transport of metals in non-acidic river systems of the Lake Baikal basin: Field data and model predictions

The speciation of metals in aqueous systems is central to understanding their mobility, bioavailability, toxicity and fate. Although several geochemical speciation models exist for metals, the equilibrium conditions assumed by many of them may not prevail in field-scale hydrological systems with flowing water. Furthermore, the dominant processes and/or process rates in non-acidic systems might differ from well-studied acidic systems. We here aim to increase knowledge on geochemical processes controlling speciation and transport of metals under non-acidic river conditions. Specifically, we evaluate the predictive capacity of a speciation model to novel measurements of multiple metals and their partitioning, under high-pH conditions in mining zones within the Lake Baikal basin. The mining zones are potential hotspots for increasing metal loads to downstream river systems. Metals released from such upstream regions may be transported all the way to Lake Baikal, where increasing metal contamination of sediments and biota has been reported. Our results show clear agreement between speciation predictions and field measurements of Fe, V, Pb and Zn, suggesting that the partitioning of these metals mainly was governed by equilibrium geochemistry under the studied conditions. Systematic over-predictions of dissolved Cr, Cu and Mo by the model were observed, which might be corrected by improving the adsorption database for hydroxyapatite because that mineral likely controls the solubility of these metals. Additionally, metal complexation by dissolved organic matter is a key parameter that needs continued monitoring in the Lake Baikal basin because dependable predictions could not be made without considering its variability. Finally, our investigation indicates that further model development is needed for accurate As speciation predictions under non-acidic conditions, which is crucial for improved health risk assessments on this contaminant.

     

The relationship of dissolved Pb to some dissolved trace metals (Al, Cr, Mn, and Zn) and to dissolved nitrate and phosphate in a freshwater aquatic system in Mauritius

The relationship of some dissolved trace metals (Al, Cr, Mn, Zn, and Pb) with one another and to dissolved phosphate and nitrate in a freshwater aquatic system at Flic en Flac and Grand River North West (GRNW) in Mauritius (1850 km2, 20 degrees S and 57 degrees E, Western Indian ocean) is reported following trace metal determination using inductively coupled plasma mass spectrometry (ICP-MS). Dissolved Al (<200 ng ml(-1)), Cr (<50 ng ml(-1)), Mn (<50 ng ml(-1)), Zn (< 100 ng ml(-1)), and Pb (<50 ng ml(-1)) upstream, downstream GRNW and in the marshes and rivulet at Flic en Flac were found to be below the recommended EEC maximum admissible concentrations and within the ambient drinking water quality standards in Mauritius. Dissolved Pb was significantly positively correlated to both dissolved Cr and Zn suggesting that the cycling for dissolved Pb is linked to the cycling of both dissolved Cr and Zn along GRNW. The common influential cycling of Pb and Zn was further reinforced as both dissolved Pb and Zn were significantly positively correlated to dissolved phosphate, which suggested a biological role in the cycling of Zn and Pb. The role of biological activity or adsorption to biological systems in Pb cycling along GRNW is further suggested as dissolved Pb was significantly correlated to dissolved nitrate. The apparent absence of the dissolved Al, Cr, and Mn with dissolved nitrate and phosphate could be attributed to factors such as the lower sensitivity of the GRNW to metal uptake during biological activity during the time frame considered. The cycling of dissolved Al and Mn was also not linked to the cycling of Cr, Zn, and Pb as no significant correlation was found along GRNW.     

Geochemistry and bioavailability of metals in sediments from northern San Francisco Bay

In this study, metals (Be, Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd, Pb and Hg) in the fine-grained fraction (<63 microm) from 12 sites at different locations in northern San Francisco Bay over a year period from March 2000 to March 2001 were analyzed after acid extraction. The results showed that metal concentrations in the sediments varied from site to site, whereas some of them were found elevated with respect to the sediment of Tomales Bay, CA, which has little contamination history, indicating an enrichment of the metals in the sediment samples analyzed. Sediment toxicity and bioaccumulation evaluation by a clam species, Macoma nasuta, exposed to the sediment samples collected from the six sampling sites was carried out. The results showed that the sediment samples tested significantly reduced clam survival. Toxicity of the sediments to the clam was, in part, related to elevated metal concentrations in the sediments. In order to examine geochemistry of the metals and to understand potential correlations between metal concentrations and geochemical matrix elements of the sediments, bioavailability and toxicity of the metals, detailed analysis of metal concentrations associated with total organic carbon and the Fe-oxy-hydroxides in the sediment samples was performed. The analysis showed that sediment geochemistry appeared to influence metal bioavailability and may have important impacts on the toxicity of these metals to the clam.     

Neuronal cytotoxicity and genotoxicity induced by zinc oxide nanoparticles

Zinc oxide nanoparticles (ZnO NPs) are one of the most abundantly used nanomaterials in consumer products and biomedical applications. As a result, human exposure to these NPs is highly frequent and they have become an issue of concern to public health. Although toxicity of ZnO NPs has been extensively studied and they have been shown to affect many different cell types and animal systems, there is a significant lack of toxicological data for ZnO NPs on the nervous system, especially for human neuronal cells and tissues. In this study, the cytotoxic and genotoxic effects of ZnO NPs on human SHSY5Y neuronal cells were investigated under different exposure conditions. Results obtained by flow cytometry showed that ZnO NPs do not enter the neuronal cells, but their presence in the medium induced cytotoxicity, including viability decrease, apoptosis and cell cycle alterations, and genotoxicity, including micronuclei production, H2AX phosphorylation and DNA damage, both primary and oxidative, on human neuronal cells in a dose- and time-dependent manner. Free Zn^2 + ions released from the ZnO NPs were not responsible for the viability decrease, but their role on other types of cell damage cannot be ruled out. The results obtained in this work contribute to increase the knowledge on the genotoxic and cytotoxic potential of ZnO NPs in general, and specifically on human neuronal cells, but further investigations are required to understand the action mechanism underlying the cytotoxic and genotoxic effects observed.     

Metal-contaminated soil remediation by using sludges of the marble industry: toxicological evaluation

The major risks due to metal pollution of sediments consist of leaching to groundwater and potential toxicity to animals and/or plants. The objective of this study was to evaluate by means of an ecotoxicological approach the effects of the addition of cutting marble sludges on the mobile metal fraction of sediments polluted with heavy metals. The study was carried out on two sediments derived from mining activities in Portman Bay (SE, Spain) polluted by heavy metals. These sediments were mixed with sludges left after the cutting of marble. The results obtained by leaching experiments showed that the addition of marble cutting sludge, consisting mainly of carbonates, to a heavy-metal polluted sediment produces a decrease of available metal forms. The carbonate content seems to play a role in chemical stabilisation of metals and in a decrease of toxicity of sediments. The leached solutions have a non-toxic effect. The mild remediation by addition of sludge has moreover effects to long term.     

A critical review of the bioavailability and impacts of heavy metals in municipal solid waste composts compared to sewage sludge

The content, behaviour and significance of heavy metals in composted waste materials is important from two potentially conflicting aspects of environmental legislation in terms of: (a) defining end-of-waste criteria and increasing recycling of composted residuals on land and (b) protecting soil quality by preventing contamination. This review examines the effects of heavy metals in compost and amended soil as a basis for achieving a practical and sustainable balance between these different policy objectives, with particular emphasis on agricultural application. All types of municipal solid waste (MSW) compost contain more heavy metals than the background concentrations present in soil and will increase their contents in amended soil. Total concentrations of heavy metals in source-segregated and greenwaste compost are typically below UK PAS100 limits and mechanical segregated material can also comply with the metal limits in UK PAS100, although this is likely to be more challenging. Zinc and Pb are numerically the elements present in the largest amounts in MSW-compost. Lead is the most limiting element to use of mechanically-segregated compost in domestic gardens, but concentrations are typically below risk-based thresholds that protect human health. Composted residuals derived from MSW and greenwaste have a high affinity for binding heavy metals. There is general consensus in the scientific literature that aerobic composting processes increase the complexation of heavy metals in organic waste residuals, and that metals are strongly bound to the compost matrix and organic matter, limiting their solubility and potential bioavailability in soil. Lead is the most strongly bound element and Ni the weakest, with Zn, Cu and Cd showing intermediate sorption characteristics. The strong metal sorption properties of compost produced from MSW or sewage sludge have important benefits for the remediation of metal contaminated industrial and urban soils. Compost and sewage sludge additions to agricultural and other soils, with background concentrations of heavy metals, raise the soil content and the availability of heavy metals for transfer into crop plants. The availability in soil depends on the nature of the chemical association between a metal with the organic residual and soil matrix, the pH value of the soil, the concentration of the element in the compost and the soil, and the ability of the plant to regulate the uptake of a particular element. There is no evidence of increased metal release into available forms as organic matter degrades in soil once compost applications have ceased. However, there is good experimental evidence demonstrating the reduced bioavailability and crop uptake of metals from composted biosolids compared to other types of sewage sludge. It may therefore be inferred that composting processes overall are likely to contribute to lowering the availability of metals in amended soil compared to other waste biostabilisation techniques. The total metal concentration in compost is important in controlling crop uptake of labile elements, like Zn and Cu, which increases with increasing total content of these elements in compost. Therefore, low metal materials, which include source-segregated and greenwaste composts, are likely to have inherently lower metal availabilities overall, at equivalent metal loading rates to soil, compared to composted residuals with larger metal contents. This is explained because the compost matrix modulates metal availability and materials low in metals have stronger sorption capacity compared to high metal composts. Zinc is the element in sewage sludge-treated agricultural soil identified as the main concern in relation to potential impacts on soil microbial activity and is also the most significant metal in compost with regard to soil fertility and microbial processes. However, with the exception of one study, there is no other tangible evidence demonstrating negative impacts of heavy metals applied to soil in compost on soil microbial processes and only positive effects of compost application on the microbial status and fertility of soil are reported. The negative impacts on soil microorganisms apparent in one long-term field experiment could be explained by the exceptionally high concentrations of Cd and other elements in the applied compost, and of Cd in the compost-amended soil, which are unrepresentative of current practice and compost quality. The metal contents of source-segregated MSW or greenwaste compost are smaller compared to mechanically-sorted MSW-compost and sewage sludge, and low metal materials also have the smallest potential metal availabilities. Composting processes also inherently reduce metal availability compared to other organic waste stabilisation methods. Therefore, risks to the environment, human health, crop quality and yield, and soil fertility, from heavy metals in source-segregated MSW or greenwaste-compost are minimal. Furthermore, composts produced from mechanically-segregated MSW generally contain fewer metals than sewage sludge used as an agricultural soil improver under controlled conditions. Consequently, the metal content of mechanically-segregated MSW-compost does not represent a barrier to end-use of the product. The application of appropriate preprocessing and refinement technologies is recommended to minimise the contamination of mechanically-segregated MSW-compost as far as practicable. In conclusion, the scientific evidence indicates that conservative, but pragmatic limits on heavy metals in compost may be set to encourage recycling of composted residuals and contaminant reduction measures, which at the same time, also protect the soil and environment from potentially negative impacts caused by long-term accumulation of heavy metals in soil.     

Riverine transfer of heavy metals from Patagonia to the southwestern Atlantic Ocean

The occurrence and geochemical behaviour of Fe, Mn, Pb, Cu, Ni, Cr, Zn and Co are studied in riverine detrital materials transported by Patagonian rivers. Their riverine inputs have been estimated and the nature of these inputs to the Atlantic Ocean is discussed. Most of the metals are transported to the ocean via the suspended load; there is evidence that Fe oxides and organic matter are important phases controlling their distribution in the detrital non-residual fraction. Most heavy metal concentrations found in bed sediments, in suspended matter, and in the dissolved load of Patagonian rivers were comparable to those reported for non-polluted rivers. There is indication that human activity is altering riverine metal inputs to the ocean. In the northern basins – and indicating anthropogenic effects – heavy metals distribution in the suspended load is very different from that found in bed sediments. The use of pesticides in the Negro River valley seems correlated with increased riverine input of Cu, mostly bound to the suspended load. The Deseado and Chico Rivers exhibit increased specific yield of metals as a consequence of extended erosion within their respective basins. The Santa Cruz is the drainage basin least affected by human activity and its metal-exporting capacity should be taken as an example of a relatively unaffected large hydrological system. In contrast, coal mining modifies the transport pattern of heavy metals in the Gallegos River, inasmuch as they are exported to the coastal zone mainly as dissolved load. Electronic Publication     

Heavy metals in mullet, Liza abu, and catfish, Silurus triostegus, from the Atatürk Dam Lake (Euphrates), Turkey

The distribution of some heavy metals in three different organs of mullet, Liza abu, and catfish, Silurus triostegus, from Atatürk Dam Lake located on Euphrates (Turkey) was studied. Co and Mo concentrations were below limits of detection in all fish organs, whereas Ni was also below limits in organs of mullet. The metal accumulation in the liver and gill of L. abu and S. triostegus was found to be quite high in comparison with the muscle. In general, the concentrations are similar to those previously observed on other fish studied in Atatürk Dam Lake and lower than those determined in Tigris River. The analysed metals (Co, Cu, Fe, Mn, Mo, Ni and Zn) were found in fish muscle at mean concentrations under the permissible limits proposed by FAO.     

Influence of alumina coating on characteristics and effects of SiO2 nanoparticles in algal growth inhibition assays at various pH and organic matter contents

Silica nanoparticles (NPs) belong to the industrially most important NP types. In a previous study it was shown that amorphous SiO(2) NPs of 12.5 and 27.0 nm are stable in algal growth inhibition assays and that their ecotoxic effects are related to NP surface area. Here, it was hypothesized and demonstrated that an alumina coating completely alters the particle-particle, particle-test medium and particle-algae interactions of SiO(2) NPs. Therefore, stability and surface characteristics, dissolution, nutrient adsorption and effects on algal growth rate of both alumina coated SiO(2) NPs and bare SiO(2) NPs in OECD algal test medium as a function of pH (6.0-8.6) and natural organic matter (NOM) contents (0-12 mg C/l) were investigated. Alumina coated SiO(2) NPs aggregated in all media and adsorbed phosphate depending on pH and NOM concentration. On the other hand, no aggregation or nutrient adsorption was observed for the bare SiO(2) NPs. Due to their positive surface charge, alumina coated SiO(2) NPs agglomerated with Pseudokirchneriella subcapitata. Consequently, algal cell density measurements based on cell counts were unreliable and hence fluorescent detection of extracted chlorophyll was the preferred method. Alumina coated SiO(2) NPs showed lower toxicity than bare SiO(2) NPs at concentrations ≥46 mg/l, except at pH 6.0. At low concentrations, no clear pH effect was observed for alumina coated SiO(2) NPs, while at higher concentrations phosphate deficiency could have contributed to the higher toxicity of those particles at pH 6.0-6.8 compared to higher pH values. Bare SiO(2) NPs were not toxic at pH 6.0 up to 220 mg/l. Addition of NOM decreased toxicity of both particles. For SiO(2) NPs the 48 h 20% effect concentration of 21.8 mg/l increased 2.6-21 fold and a linear relationship was observed between NOM concentration and effective concentrations. No effect was observed for alumina coated SiO(2) NPs in presence of NOM up to 1000 mg/l. All experiments point out that the alumina coating completely altered NP interactions. Due to the difference in surface composition the SiO(2) NPs, which had the smallest surface area, were more toxic to the alga than the alumina coated SiO(2) NPs. Hence, surface modification can dominate the effect of surface area on toxicity.     

Comparative chronic toxicity of nanoparticulate and ionic zinc to the earthworm Eisenia veneta in a soil matrix

Manufactured nanoparticles (NPs) are increasingly being used in a range of consumer products and are already entering the environment. NP ZnO is one of the most widely used and potentially toxic NPs in aquatic exposures. It is likely that ZnO nanoparticles will also be bioavailable to soil organisms, studies on ZnO NP toxicity in a soil matrix are lacking. We exposed the earthworm Eisenia veneta to uncoated NP ZnO (<100 nm) dosed to soil and food at 250 and 750 mg Zn kg(-1) for 21 d. Concurrent exposures of equivalent ionic Zn were conducted with ZnCl(2) and for both forms effects on life history traits, immune activity and Zn body concentrations were compared. Despite slightly higher measured body concentrations, NP ZnO generally had less impact than ZnCl(2) on measured traits. At 750 mg Zn kg(-1), reproduction declined by 50% when exposed to NP ZnO but was almost completely inhibited by ZnCl(2). Similarly, immune activity was unaffected by NP ZnO but was suppressed by 20% when exposed to ZnCl(2). Scanning electron microscopy analysis of worm tissues following 24h aqueous exposure showed the presence of ZnO particles suggesting that NPs can be taken up in particulate form. This may explain the reduced effects at similar body concentrations seen in the soil study. Our findings suggest that risk assessments do not need to go beyond considering the metal component of NP ZnO in soils at least for the larger size uncoated particles considered here.