Bioavailable iron concentrations regulate phytoplankton growth and bloom formation in low-nutrient lakes.

The growth of phytoplankton in lakes is thought to be primarily controlled by macronutrient concentrations, but the availability of trace metal micronutrients, such as iron (Fe), are increasingly recognised as important regulators of lake primary production. This study evaluates the role of Fe in regulating phytoplankton growth in lakes of different nutrient status in New Zealand. The results of this unique year-long study, combining highly sensitive trace metal concentration analysis of waters and particulates with advanced trace metal bioavailability and speciation modelling, constrains thresholds for bioavailable Fe and colloidal Fe of 0.8 nmol·L-1 and 30 nmol·L-1, respectively, below which phytoplankton growth-limitation occurs. These thresholds specifically control diatom bloom formation and termination in lakes, thereby exerting a strong influence on freshwater carbon sequestration, given the dominance of diatoms in lake bloom assemblages. Importantly, potentially toxic cyanobacteria thrived only after events of bottom water anoxia, when additional dissolved Fe in concentrations ≥4 nmol·L-1 was released into the water column. These new thresholds for bioavailable and colloidal Fe offer the potential to manage micronutrient levels in lakes for the purpose of regulating algal bloom formation and carbon sequestration, while at the same time, suppressing the formation of harmful cyanobacterial blooms.

Soil cadmium mobilisation by dissolved organic matter from soil amendments.

Dissolved organic matter (DOM) release from Cd contaminated soils been linked to mobilisation of the metal as Cd-DOM complexes and this may be exacerbated by organic matter-rich soil amendments. The quantity and quality of the DOM can determine the proportion of dissolved Cd that partitions to mobile complexes and their stability and, thus, the potential for Cd transport from contaminated soils. The aim of this work was to examine differences in Cd mobilisation from soils to which different types of soil amendments/conditioners have been applied and the importance of DOM characteristics in determining the extent to which this can happen. Three soils were spiked with Cd to 2 mg kg-1, allowed to equilibrate and then treated with compost and peat. These soils and an untreated subsample of each soil were then adjusted to three different pHs: 5.6, 6.4 and 7.4, using lime. The amount of Cd mobilised from each soil was tested using a column leaching experiment. Ultrafiltration and speciation modelling were used to determine amounts of Cd as DOM-complexed, "truly" dissolved (<5 kDa) and colloidal species, while DOM quality was assessed using UV-Vis and fluorescence spectroscopy. Most colloidal Cd was mobilised from the compost treated soils (50%-60%), followed by the peat treated soils (20-44%). The relationships between colloidal Cd, DOC concentration and soil pH, together with the spectroscopic and modelling results showed that structural properties of DOM are an important factor in mobilising Cd from contaminated soils.

Transport and speciation of uranium in groundwater-surface water systems impacted by legacy milling operations.

Growing worldwide concern over uranium contamination of groundwater resources has placed an emphasis on understanding uranium transport dynamics and potential toxicity in groundwater-surface water systems. In this study, we utilized novel in-situ sampling methods to establish the location and magnitude of contaminated groundwater entry into a receiving surface water environment, and to investigate the speciation and potential bioavailability of uranium in groundwater and surface water. Streambed temperature mapping successfully identified the location of groundwater entry to the Little Wind River, downgradient from the former Riverton uranium mill site, Wyoming, USA. Diffusive equilibrium in thin-film (DET) samplers further constrained the groundwater plume and established sediment pore water solute concentrations and patterns. In this system, evidence is presented for attenuation of uranium-rich groundwater in the shallow sediments where surface water and groundwater interaction occurs. Surface water grab and DET sampling successfully detected an increase in river uranium concentrations where the groundwater plume enters the Little Wind River; however, concentrations remained below environmental guideline levels. Uranium speciation was investigated using diffusive gradients in thin-film (DGT) samplers and geochemical speciation modelling. Together, these investigations indicate uranium may have limited bioavailability to organisms in the Little Wind River and, possibly, in other similar sites in the western U.S.A. This could be due to ion competition effects or the presence of non- or partially labile uranium complexes. Development of methods to establish the location of contaminated (uranium) groundwater entry to surface water environments, and the potential effects on ecosystems, is crucial to develop both site-specific and general conceptual models of uranium behavior and potential toxicity in affected ground and surface water environments.

Environmental and edaphic factors affecting soil cadmium uptake by spinach, potatoes, onion and wheat.

The relative ease with which cadmium (Cd) in agricultural soils can transfer to crop plants can pose a potential health risk to consumers. However, efforts to predict and mitigate these risks are often confounded by the various factors that influence metal accumulation in the edible plant parts. The aim of this work was to identify key drivers that determine Cd concentrations in spinach leaves, potato tubers, onion bulbs and wheat grain grown in commercial horticultural operations across New Zealand (NZ). Paired soil and plant samples (n = 147) were collected from farms across different NZ growing regions. Cadmium concentrations in the edible parts were measured and four different tests were used to examine the potential bioavailability of soil Cd: pseudo-total and porewater concentrations, 0.05 M Ca(NO3)2-extraction and diffusive gradients in thin-films (DGT). Information on a range of soil and climatic variables was also collected. The methods' ability to represent Cd concentrations in the plant parts was assessed through single and multiple regression analysis that considered the different variables and the farm locations. Soil Cd concentrations determined by the different tests were positively related to plant concentrations and there were clear regional differences between these relationships. The Ca(NO3)2 extraction predicted over 76% of the variability in Cd concentrations in onion bulbs and spinach leaves, while DGT and porewater Cd provided the best estimates for potato tubers and wheat grains, respectively, once regional differences were considered, along with certain environmental and soil variables. The results show that certain soil and environmental factors can be a key influence for determining Cd accumulation in the edible parts of some plants and that regional differences are important for modulating the extent to which this occurs. These effects should be considered when trying to mitigate the potential risks arising from Cd in agricultural soils.

Environmental Parameters Affecting the Concentration of Iodine in New Zealand Pasture.

Iodine (I) is an essential trace element commonly deficient in agricultural systems. Whereas there is much information on I in food crops, there is a lacuna of knowledge on the environmental factors that affect pasture I concentrations. We aimed to identify the most important environmental factors affecting the concentration of I in New Zealand pastures, and the consequences to agricultural systems. Soil and pastoral samples were collected throughout the country and analyzed for I and other elements. The soils contained 1.1 to 86 mg I kg, with 0.005 to 1.4 mg kg in the pasture. In 26% of pastures, I concentrations were insufficient for sheep nutrition, whereas 87% contained insufficient I for cattle nutrition. Pasture I concentrations were negatively correlated with the distance from the sea, and the concentration of oxalate-extractable amorphous Al, Fe, and Si oxides, which immobilize soil I. Soil organic C and clay increased I retention in soil but did not significantly affect pasture I concentrations. Future work should investigate how soil properties affect pasture I uptake in inland areas.

Cadmium Concentrations in New Zealand Wheat: Effect of Cultivar Type, Soil Properties, and Crop Management.

Wheat ( L.) grain is a contributing source of dietary Cd in New Zealand, but despite this, there is a dearth of information on Cd concentrations in wheat and the factors that affect uptake. We measured Cd concentrations in 12 wheat cultivars grown in field sites across New Zealand and also assessed the soil, plant, and crop factors that have been reported to affect Cd uptake. We found there was a wide range in grain Cd concentrations (0.004 to 0.205 mg kg fresh weight [FW]). The overall mean concentration (0.066 mg kg FW) was below the maximum limit (ML) of 0.1 mg kg FW. Only 7% of grain samples across seven sites exceeded the ML. There were significant ( < 0.05) differences (2.5-fold) in Cd concentrations in wheat grain between cultivars. No strong significant relationships were found between soil properties and Cd concentrations in grain. Further, management factors affecting grain Cd concentrations were inconsistent. Given the lack of relationships between soils and management practices, the most effective way of limiting Cd uptake in wheat grain at sites where Cd exceeds MLs may be the use of low-Cd-accumulating cultivars. Further studies are required to explore specifically the influence of irrigation and effects of type and rate of fertilizer on Cd uptake in wheat, as well as to better understand the mechanisms of Cd uptake in wheat.

Simultaneous Quantification of Soil Phosphorus Labile Pool and Desorption Kinetics Using DGTs and 3D-DIFS.

The buffering of phosphorus concentrations in soil solution by the soil-solid phase is an important process for providing plant root access to nutrients. Accordingly, the size of labile solid phase-bound phosphorus pool and the rate at which it can resupply phosphorous into the dissolved phase can be important variables in determining when the plant availability of the nutrient may be limited. The phosphorus labile pool (Plabile) and its desorption kinetics were simultaneously evaluated in 10 agricultural UK soils using the diffusive gradients in thin-films (DGT) technique. The DGT-induced fluxes in the soil and sediments model (DIFS) was fitted to the time series of DGT deployments (1-240 h), which allowed the estimation of Plabile, and the system response time ( Tc). The Plabile concentration was then compared to that obtained by several soil P extracts including Olsen P, FeO-P, and water extractable P, in order to assess if the data from these analytical procedures can be used to represent the labile P across different soils. The Olsen P concentration, commonly used as a representation of the soil labile P pool, overestimated the desorbable P concentration by 6-fold. The use of this approach for the quantification of soil P desorption kinetic parameters found a wide range of equally valid solutions for Tc. Additionally, the performance of different DIFS model versions working in different dimensions (1D, 2D, and 3D) was compared. Although all models could provide a good fit to the experimental DGT time series data, the fitted parameters showed a poor agreement between different model versions. The limitations of the DIFS model family are associated with the assumptions taken in the modeling approach and the three-dimensional (3D) version is here considered to be the most precise among them.

Response of a Pioneering Species (Leptospermum scoparium J.R.Forst. & G.Forst.) to Heterogeneity in a Low-Fertility Soil.

Root foraging may increase plant nutrient acquisition at the cost of reducing the total volume of soil explored, thereby reducing the chance of the roots encountering additional patches. Patches in soil seldom contain just one nutrient: the patch may also have distinct textural, hydrological, and toxicological characteristics. We sought to determine the characteristics of root foraging by a pioneering species, Leptospermum scoparium, using pot trials and rhizobox experiments with patches of biosolids. The growth of L. scoparium was increased by <50 t/ha equiv. of biosolids but higher doses were inhibitory. Roots foraged patches of biosolids in a low-fertility soil. There was no evidence of chemotaxis, rather, the roots proliferated toward the patch of biosolids, following chemical gradients of nitrate. While the biosolids also contained high concentrations of other nutrients (P, K, and S), only significant chemical gradients of nitrate were found. Once the roots encountered a patch of biosolids, the growth of the plant increased to a level similar to plants growing in soil homogeneously mixed with biosolids or surface-applied biosolids. Our results indicate that roots forage nitrate, which is mobile in soil, and that gradients of nitrate may lead to patches containing other less mobile nutrients, such as phosphate or potassium.

The mobility and plant uptake of gallium and indium, two emerging contaminants associated with electronic waste and other sources.

Gallium (Ga) and indium (In) are increasingly susceptible to soil contamination via disposal of electronic equipment. Chemically similar to aluminium (Al), these elements may be mobile and bioavailable under acidic conditions. We sought to determine extent and nature of Ga and In mobility in the soil - plant system and thus their potential to enter the food chain. Batch sorption experiments on a high fertility silt loam (pH 5.95, CEC 22 meq 100 g-1) showed strong retention of both elements to the soil matrix, with mean distribution coefficient (KD) values of 408 and 2021 L kg-1 for Ga and In respectively. KD increased with concentration, which we attributed to precipitation of excess ions as insoluble hydroxides. KD decreased with increased pH as Ga/In(OH)2+ and Ga/In(OH)2+ transitioned to Ga/In(OH)4-. Movement into the aboveground portions of perennial ryegrass (Lolium perenne L.) was low, with bioaccumulation factors of 0.0037 for Ga and 0.0002 for In; foliar concentrations peaked at 11.6 mg kg-1 and 0.015 mg kg-1 respectively. The mobility of Ga and In in the soil - plant system is low compared to other common trace element contaminants such as cadmium, copper, and zinc. Therefore, Ga and In are likely to accumulate in soils and soil ingestion, either directly, via inhaled dust, or dust attached to food, will be the largest pathway into the food chain. Future work should focus on the effect of redox conditions on Ga and In, as well as uptake into acidophilic plants such as Camellia spp., which accumulate Al.

Trace metal mobilization by organic soil amendments: insights gained from analyses of solid and solution phase complexation of cadmium, nickel and zinc.

The accumulation of Cd in soils worldwide has increased the demand for methods to reduce the metal's plant bioavailability. Organic matter rich soil amendments have been shown to be effective in achieving this. However, it is not known how long these amendments can retain the Cd, and whether dissolved organic matter (DOM) released from them can enhance the metal's mobility in the environment. In this study we sought to test the Cd binding capacity of various organic soil amendments, and evaluate differences in characteristics of the DOM released to see if they can explain the lability of the Cd-DOM complexes. We collected ten organic soil amendments from around New Zealand: five different composts, biosolids from two sources, two types of peat and spent coffee grounds. We characterised the amendments' elemental composition and their ability to bind the Cd. We then selected two composts and two peats for further tests, where we measured the sorption of Ni or Zn by the amendments. We analysed the quality of the extracted DOM from the four amendments using 3D Excitation Emission Matrix analysis, and tested the lability of the metal-DOM complexes using an adapted diffusive gradients in thin-films (DGT) method. We found that composts bound the most Cd and that the emergent Cd-DOM complexes were less labile than those from the peats. Ni-DOM complexes were the least labile. The aromaticity of the extracted DOM appears to be an important factor in determining the lability of Ni complexes, but less so for Zn and Cd.

A mesocosm study of oxygen and trace metal dynamics in sediment microniches of reactive organic material.

Deposition of particulate organic matter (POM) induces diagenetic hot spots at the sediment-water interface (SWI). Here we explore the effects of intensive POM degradation for metal mobilization at the SWI. By using a combined planar optode-DGT (diffusive gradient in thin-films) sensor we obtained simultaneous measurements of dissolved O2 and trace metal dynamics around an aggregate of reactive organic matter placed on the SWI of a sediment mesocosm. The aggregate induced a rapid, highly localized, decrease in O2 concentration, resulting in an anoxic feature at the SWI. Co-located with this feature, we observed intense Fe and Mn mobilization, removal of Co, Ni and Zn and found evidence for the concurrent release and precipitation of Pb within a small confined volume. We also identified two small microniches in the anoxic sediment below the SWI, defined by elevated trace metal mobilization. Differences between the metal release rates in these two microniches indicate that they were formed by the mineralisation of different types of organic matter buried in the sediment. Our results provide direct empirical evidence for the potential importance of POM-induced reactive microniches when considering the fluxes of metals from and within aquatic sediments, and suggest that other elements' cycles may also be affected.

Effects of Lime and Organic Amendments Derived from Varied Source Materials on Cadmium Uptake by Potato.

Repeated applications of Cd-rich phosphate fertilizers have resulted in elevated concentrations of this toxic element in some New Zealand soils. Exceedance of the food safety standard for Cd (0.1 mg kg fresh weight) has been reported for potato ( L.). Composts may efficiently sorb Cd in soil and therefore reduce its phytoavailability, leading to reduced uptake by plants. We aimed to determine the potential of various composts, shredded corn stover, and lime at two different rates to reduce the transfer of Cd from a soil (containing 1.45 mg kg Cd) to potato (var. 'Nadine'). In the control, the peeled tubers, skins, leaves, and stems had Cd concentrations of 0.04, 0.09, 0.26, and 0.53 mg kg dry weight, respectively. There was a 71% reduction in tuber Cd concentrations in potatoes grown in soil amended with 5% (w/w) shredded corn stover, although it significantly decreased potato biomass. Potatoes grown in soil amended with pig manure compost, mushroom compost, sawdust-animal waste compost, and municipal compost at rates of either 2.5 or 5% (w/w) reduced tuber Cd concentrations by 58 to 66%, 46 to 63%, 52 to 53%, and 29 to 49%, respectively. Lime (1.3%) application in soil reduced tuber Cd concentrations by 50%. Composts significantly increased tuber biomass. Further work is warranted to identify the key components of composts that result in reduced Cd uptake by plants.

Localized flux maxima of arsenic, lead, and iron around root apices in flooded lowland rice.

In wetland-adapted plants, such as rice, it is typically root apexes, sites of rapid entry for water/nutrients, where radial oxygen losses (ROLs) are highest. Nutrient/toxic metal uptake therefore largely occurs through oxidized zones and pH microgradients. However, the processes controlling the acquisition of trace elements in rice have been difficult to explore experimentally because of a lack of techniques for simultaneously measuring labile trace elements and O2/pH. Here, we use new diffusive gradients in thin films (DGT)/planar optode sandwich sensors deployed in situ on rice roots to demonstrate a new geochemical niche of greatly enhanced As, Pb, and Fe(II) mobilization into solution immediately adjacent to the root tips characterized by O2 enrichment and low pH. Fe(II) mobilization was congruent to that of the peripheral edge of the aerobic root zone, demonstrating that the Fe(II) mobilization maximum only developed in a narrow O2 range as the oxidation front penetrates the reducing soil. The Fe flux to the DGT resin at the root apexes was 3-fold higher than the anaerobic bulk soil and 27 times greater than the aerobic rooting zone. These results provide new evidence for the importance of coupled diffusion and oxidation of Fe in modulating trace metal solubilization, dispersion, and plant uptake.

An evaluation of DGT performance using a dynamic numerical model.

A numerical model of the transport and dynamics of metal complexes in the resin and gel layers of a DGT (diffusive gradients in thin films) device was developed and used to investigate how the chelating resin and metal-ligand complexes in solution affect metal uptake. Decreasing the stability constant or concentration of the binding resin increases the competition for free metal ions by ligands in solution, lowering the rate of mass uptake. Such effects would be rarely observed for moderately or strongly binding resins (K> 10(12)), including Chelex, which out-compete labile ligands in solution. With weakly binding resins, strongly bound solution complexes can diffuse into the resin layer before a measurable amount of dissociation occurs, such that concentrations of bound metal at the rear and front surfaces of the resin layer are equal. With more strongly binding resins, metal mainly binds to the front surface of the resin. Only complexes with the largest binding constants penetrate the gel layer containing Chelex, buttheir lack of lability means thatthe DGT sensitivity to the complex is, in any case, very low. The slow diffusion of complexes, such as those of fulvic acids, which increases the time required to establish steady state, compromises the use of the simple DGT equation. Errors are negligible for 24 h deployments, when diffusive layer thicknesses are less than 1 mm, but 3 day deployments are required to ensure accuracy with 2.4 mm thick layers. The extent to which the commonly used equation, that accounts for the concentration and diffusion of metal-complex species, overestimates DGT uptake if the rate of dissociation is slow, was estimated.

Dynamic aspects of DGT as demonstrated by experiments with lanthanide complexes of a multidentate ligand.

Sampling of metals with the technique of diffusive gradients in thin-films (DGT) depends on the rates of diffusion and on the kinetics of interconversion of the species present. In this study the discrimination between metal complexes with different dissociation kinetics is investigated. Samplers with differentthicknesses of diffusive and resin gels were deployed in solutions containing 10 microg/L of each metal in the lanthanide (Ln) series (except Pm) and 2.0 x 10(-6) M of the ligand quin2 at an ionic strength of 0.1 M (KNO3) and pH 7.0. Diffusion coefficients of Ln3+ ions and Ln-quin2 complexes were determined in a diffusion cell experiment. The equilibrium speciation of the metals was calculated from available stability constants. The sampling rate (mass/time) was highly dependent on the dissociation-rate constant of the complexes. For complexes with dissociation kinetics that appreciably limited the uptake, the sampling rate decreased significantly with increasing deployment times (12, 24, and 76 h) and was virtually independent of the thickness of the diffusive gel. Placing a layer of diffusive gel behind the resin did not influence the accumulation of Lns in the resin gel, but doubling the thickness of the layer containing resin increased the uptake, and more so for the Lns forming less labile complexes. The Lns forming more labile complexes were enriched in the outer layer of the resin, and there was a trend toward even distribution between the outer and deeper parts of the resin layer for the Lns forming less labile complexes. The measured DGT sampling rates (mass/ time) were reasonably well predicted by a dynamic model that used independently determined kinetic constants. This new knowledge of how metal complexes behave in the sampling process paves the way for using DGT to obtain in situ kinetic information in natural waters.