Mike J. McLaughlin

Nanomaterials in the environment: Behavior, fate, bioavailability, and effects

The recent advances in nanotechnology and the corresponding increase in the use of nanomaterials in products in every sector of society have resulted in uncertainties regarding environmental impacts. The objectives of this review are to introduce the key aspects pertaining to nanomaterials in the environment and to discuss what is known concerning their fate, behavior, disposition, and toxicity, with a particular focus on those that make up manufactured nanomaterials. This review critiques existing nanomaterial research in freshwater, marine, and soil environments. It illustrates the paucity of existing research and demonstrates the need for additional research. Environmental scientists are encouraged to base this research on existing studies on colloidal behavior and toxicology. The need for standard reference and testing materials as well as methodology for suspension preparation and testing is also discussed.

METALS AND MICRONUTRIENTS – FOOD SAFETY ISSUES

Abstract Of all the elements, the most important to consider in terms of food-chain contamination are arsenic (As), cadmium (Cd), mercury (Hg), lead (Pb) and selenium (Se). Where soils are enriched in these elements, it is usually through the agricultural, industrial or urban activities of man, except for Se where high concentrations in soil are often derived from high-Se parent rock materials. The propensity for plants to accumulate and translocate these contaminants to edible and harvested parts depends largely on soil and climatic factors, plant genotype and agronomic management. Elevated As intake, especially of inorganic As, is most likely to arise from high-As drinking water than from ingestion of food. Cadmium and Se are of the greatest concern in terms of terrestrial food-chain contamination, with the former element receiving most attention. Worldwide, the probability of insufficient Se in the human diet exceeds that of toxicity, with deficiency usually associated with monotonous vegetarian diets in areas with Se-deficient soils. Excessive human intake of Cd is of concern as this element accumulates over a lifetime in the body, with impairment of kidney function being the main adverse effect. Cadmium inputs to soil in fertilizer, biosolids, soil amendments and atmospheric deposition often exceed outputs in crops and drainage waters, so that Cd concentrations in many agricultural soils are slowly increasing. However, evidence for increases in Cd concentrations in crops over time is contentious, as is the evidence for human health problems due to low-level Cd contamination of the food chain. Adverse health effects due to Cd intake have been manifest only in situations of gross soil contamination, with a predominantly rice-based diet, where soil–plant and plant–human transfer of Cd would have been enhanced. Human feeding studies have indicated that food Cd bioavailability is dependent on Fe nutrition, and animal studies have indicated that Zn, Ca, P and other elements and food constituents (e.g. fiber, phytate) affect Cd bioavailability. While plant breeding and agronomic management can minimize soil–plant transfer of Cd, and maximize concentrations of antagonists to Cd assimilation in humans, it remains important that inputs of this metal to soil be minimized.

Cadmium in Soils and Plants

Of all the non-essential heavy metals, cadmium (Cd) is perhaps the metal which has attracted most attention in soil science and plant nutrition due to its potential toxicity to man, and the relative mobility in the soil-plant system. Schroeder and Balassa (1963) were among the first researchers to highlight the potential concern for Cd accumulation in the food chain, through Cd impurities in fertilisers and amendments applied to soils. Interest in Cd in soils and plants was further stimulated when industrial pollution of agricultural lands in Japan with Cd-rich waste waters led to serious human health problems (“Itai-itai” disease), first documented in the 1970’s (Kobayashi, 1978; Takeuchi, 1978). This topic will be further discussed in Chapter 10.

Soil testing for heavy metals.

Abstract Soil testing for metal contaminants is a continually evolving process aimed at improving the assessment of environmental and human health hazards associated with heavy metals in soils and plants. A number of challenges present themselves before accurate, reliable and precise contaminant hazard assessment criteria for soils and plants can be made. These include: sampling, extraction and analytical obstacles associated with the determination of trace levels of metals in environmental media; quality assurance and quality control issues associated with both extraction and analytical procedures (especially for metals where non‐compliance with regulatory standards may be penalised); and confounding environmental effects (e.g. rooting depth, soil salinity, Eh, pH, plant species, metal species) which limit the usefulness of the relationship between the current tests and actual hazards. These difficulties have combined to produce soil tests for heavy metals often poorly correlated with hazardwhether this be crop uptake of a contaminant (e.g. Cd), or the adverse effects of metals or metalloids on human or environmental health (e.g. As, Cr, Cu, Hg, Ni, Se, Pb, Zn). Assessment of an “available” fraction of a particular soil nutrient is the accepted norm of soil testing for crop nutrition. In many countries, assessment of metal hazard is still inappropriately based on the total soil metal concentration, despite increasing recognition that the concept of elemental availability is just as relevant for environmental hazard as for crop nutrition. Tests that aim to assess metal “bioavailability” are now gaining widespread acceptance by regulators as a means to characterise hazards from contaminants in soil. While a significant advance on the use of total metal concentrations, the concept raises difficulties in providing an adequate assessment of potential risk, due to changes in environmental conditions which affect bioavailability, e.g. soil pH, soil organic matter content. This chapter summarises current soil testing methodologies for metal contaminants and examines new concepts and procedures for assessing hazards from metal contamination of soils.

Review: A bioavailability-based rationale for controlling metal and metalloid contamination of agricultural land in Australia and New Zealand

Metal pollution of agricultural land in Australia and New Zealand is less severe than that documented in many European countries, due to the lower density of urban developments and a lower level of industrialisation. However, Australia and New Zealand are highly dependent on plant production systems based on plant-microbial symbioses (e.g. Rhizobium, mycorrhizae) and other natural biogeochemical processes for maintaining nutrient status in soils that are generally low in nutrients and, in Australia, also low in organic matter. Data linking metal concentrations in soil to agricultural and ecological effects are sparse for Australia and New Zealand, and regulatory frameworks and guidelines to control metal contamination of soils rely heavily on data generated in countries of the northern hemisphere. Adoption of benchmark concentrations for metal contaminants from these countries has led to inappropriate levels being chosen for several elements. These problems could be avoided and metal contamination of soils could be more effectively controlled if instead of relying on total concentrations of metals in soil and soil amendments, regulations and guidelines considered the biologically active fractions. This review considers the advantages and disadvantages of a bioavailability-based approach to the control of metal contamination of soils and suggests improvements needed to avoid both over- and under-protective measures.

Fate and Risks of Nanomaterials in Aquatic and Terrestrial Environments

Over the last decade, nanoparticles have been used more frequently in industrial applications and in consumer and medical products, and these applications of nanoparticles will likely continue to increase. Concerns about the environmental fate and effects of these materials have stimulated studies to predict environmental concentrations in air, water, and soils and to determine threshold concentrations for their ecotoxicological effects on aquatic or terrestrial biota. Nanoparticles can be added to soils directly in fertilizers orplant protection products or indirectly through application to land or wastewater treatment products such as sludges or biosolids. Nanoparticles may enter aquatic systems directly through industrial discharges or from disposal of wastewater treatment effluents or indirectly through surface runoff from soils. Researchers have used laboratory experiments to begin to understand the effects of nanoparticles on waters and soils, and this Account reviews that research and the translation of those results to natural conditions. In the environment, nanoparticles can undergo a number of potential transformations that depend on the properties both of the nanoparticle and of the receiving medium. These transformations largely involve chemical and physical processes, but they can involve biodegradation of surface coatings used to stabilize many nanomaterial formulations. The toxicity of nanomaterials to algae involves adsorption to cell surfaces and disruption to membrane transport. Higher organisms can directly ingest nanoparticles, and within the food web, both aquatic and terrestrial organisms can accumulate nanoparticles. The dissolution of nanoparticles may release potentially toxic components into the environment. Aggregation with other nanoparticles (homoaggregation) or with natural mineral and organic colloids (heteroaggregation) will dramatically change their fate and potential toxicity in the environment. Soluble natural organic matter may interact with nanoparticles to change surface charge and mobility and affect the interactions of those nanoparticles with biota. Ultimately, aquatic nanomaterials accumulate in bottom sediments, facilitated in natural systems by heteroaggregation. Homoaggregates of nanoparticles sediment more slowly. Nanomaterials from urban, medical, and industrial sources may undergo significant transformations during wastewater treatment processes. For example, sulfidation of silver nanoparticles in wastewater treatment systems converts most of the nanoparticles to silver sulfides (Ag₂S). Aggregation of the nanomaterials with other mineral and organic components of the wastewater often results in most of the nanomaterial being associated with other solids rather than remaining as dispersed nanosized suspensions. Risk assessments for nanomaterial releases to the environment are still in their infancy, and reliable measurements of nanomaterials at environmental concentrations remain challenging. Predicted environmental concentrations based on current usage are low but are expected to increase as use increases. At this early stage, comparisons of estimated exposure data with known toxicity data indicate that the predicted environmental concentrations are orders of magnitude below those known to have environmental effects on biota. As more toxicity data are generated under environmentally-relevant conditions, risk assessments for nanomaterials will improve to produce accurate assessments that assure environmental safety.

Toxicity of Trace Metals in Soil as Affected by Soil Type and Aging After Contamination: Using Calibrated Bioavailability Models to Set Ecological Soil Standards

Total concentrations of metals in soil are poor predictors of toxicity. In the last decade, considerable effort has been made to demonstrate how metal toxicity is affected by the abiotic properties of soil. Here this information is collated and shows how these data have been used in the European Union for defining predicted-no-effect concentrations (PNECs) of Cd, Cu, Co, Ni, Pb, and Zn in soil. Bioavailability models have been calibrated using data from more than 500 new chronic toxicity tests in soils amended with soluble metal salts, in experimentally aged soils, and in field-contaminated soils. In general, soil pH was a good predictor of metal solubility but a poor predictor of metal toxicity across soils. Toxicity thresholds based on the free metal ion activity were generally more variable than those expressed on total soil metal, which can be explained, but not predicted, using the concept of the biotic ligand model. The toxicity thresholds based on total soil metal concentrations rise almost proportionally to the effective cation exchange capacity of soil. Total soil metal concentrations yielding 10% inhibition in freshly amended soils were up to 100-fold smaller (median 3.4-fold, n = 110 comparative tests) than those in corresponding aged soils or field-contaminated soils. The change in isotopically exchangeable metal in soil proved to be a conservative estimate of the change in toxicity upon aging. The PNEC values for specific soil types were calculated using this information. The corrections for aging and for modifying effects of soil properties in metal-salt-amended soils are shown to be the main factors by which PNEC values rise above the natural background range.

The Performance of Visible, Near-, and Mid-Infrared Reflectance Spectroscopy for Prediction of Soil Physical, Chemical, and Biological Properties

Abstract This review addresses the applicability of visible (Vis), near-infrared (NIR), and mid-infrared (MIR) reflectance spectroscopy for the prediction of soil properties. We address (1) the properties that can be predicted and the accuracy of the predictions, (2) the most suitable spectral regions for specific soil properties, (3) the number of predictions reported for each property, and (4) in-field versus laboratory spectral techniques. We found the following properties to be successfully predicted: soil water content, texture, soil carbon (C), cation exchange capacity, calcium and magnesium (exchangeable), total nitrogen (N), pH, concentration of metals/metalloids, microbial size, and activity. Generally, MIR produced better predictions than Vis-NIR, but Vis-NIR outperformed MIR for a number of properties (e.g., biological). An advantage of Vis-NIR is instrument portability although a new range of MIR portable devices is becoming available. In-field predictions for clay, water, total organic C, extractable phosphorus, total C and N appear similar to laboratory methods, but there are issues regarding, for example, sample heterogeneity, moisture content, and surface roughness. The nature of the variable being predicted, the quality and consistency of the reference laboratory methods, and the adequate representation of unknowns by the calibration set must be considered when predicting soil properties using reflectance spectroscopy.

Chemical characteristics of phosphorus in alkaline soils from southern Australia

This study was performed to better understand the chemical behaviour of P in a variety of alkaline soils from southern Australia. To do so, surface soil samples of 47 alkaline cropping soils from Upper Eyre Peninsula in South Australia and from western Victoria were collected. The 22 soils collected from Eyre Peninsula were Calcarosols, and those from western Victoria were Vertosols, Alkaline Duplex soils, Sodosols, and Red Brown Calcareous soils. Parameters included total and amorphous Al and Fe, organic C, organic P, CaCO3 content, P sorption characteristics, phosphorus buffer capacity, calcium lactate (Ca-Lac) extractable P, bicarbonate-extractable (Colwell) P, water-extractable P, anion exchange membrane extractable P (AEM-P), and isotopically exchangeable P (labile P). Concentrations of micronutrients in the Calcarosols were relatively low, considered to be a function of low clay contents. Given very low background Cd concentrations in the soils, it was estimated from Cd measurements that the majority of total P in the soils was derived from previous fertiliser applications. Phosphorus buffer capacities (PBCs) were relatively high in the Calcarosols and moderately high in the other alkaline soils. P sorption behaviour in the Calcarosols was a direct function of CaCO3 content, although in the other alkaline soils, amorphous Al and Fe oxides were the principal determinants of the P sorption behaviour. Both Colwell and Ca-Lac extractants dissolved non-labile P in the highly calcareous soils, whereas AEM appeared to only remove surface-adsorbed P. In addition, Colwell P values were positively related to PBC and to the slope term in the Freundlich model (Kf) when Kf > 10. It is suggested that AEM-P may be a better predictor of P availability in highly calcareous soils compared with the other extractants.

Solubility and batch retention of CeO2 nanoparticles in soils.

There is a paucity of information on the environmental fate of cerium oxide nanoparticles (CeO2 NPs) for terrestrial systems that may be exposed to CeO2 NPs by the application of biosolids derived from wastewater treatment systems. Using ultrafiltration (UF), dissolution, and nonequilibrium retention (Kr) values of citrate-coated (8 nm diameter) CeO2 NPs and partitioning (Kd) values of dissolved Ce(III) and Ce(IV) were obtained in suspensions of 16 soils with a diversity of physicochemical properties. Dissolution of CeO2 NPs studied in solutions was only significant at pH 4 and was less than 3.1%, whereas no dissolved Ce was detected in soils spiked with CeO2 NPs. Kr values of CeO2 NP were low (median Kr=9.6 L kg(-1)) relative to Kd values of dissolved CeIII and CeIV (median Kd=3763 and 1808 L kg(-1), respectively), suggesting low CeO2 NP retention in soils. Surface adsorption of phosphate to CeO2 NP caused a negative zeta potential, which may explain the negative correlation of log Kr values with dissolved phosphate concentrations and the significant reduction of Kr values upon addition of phosphate to soils. The positive correlation of Kr values with clay content suggested heterocoagulation of CeO2 NPs with natural colloids in soils. Co-addition of CeO2 NPs with biosolids, on the other hand, did not affect retention.