Linkages between the concept of nature-based solutions and the notion of landscape.

As the effects of Nature-based solutions (NBS) application are usually much broader than only the area under the project implementation, it is necessary to capture the impact on these actions of landscape as well as the influence of landscape type on the NBS effectiveness. The main aim of this study was to detect linkages between the operational of NBS and the landscape dimention, based on a systematic literature review. The results showed the existence of seven linkages: (1, 2) 'input' and 'output' resulting from the consideration of landscape as a scale of NBS implementation; (3, 4) 'stimulator' and 'inspiration' based on the contribution of landscape-based management to the implementation of NBS; (5) 'co-beneficiary' since the implementation of NBS affects aesthetic dimensions of landscape; (6) 'tool' as landscape-based indicators are used to assess the impacts of NBS; and (7) 'foundation' as health-supporting landscapes may be considered as a type of NBS action.

Biological nitrification inhibition by root exudates of native species, Hibiscus splendens and Solanum echinatum.

Australian native species grow competitively in nutrient limited environments, particularly in nitrogen (N) limited soils; however, the mechanism that enables this is poorly understood. Biological nitrification inhibition (BNI), which is the release of root exudates into the plant rhizosphere to inhibit the nitrification process, is a hypothesized adaptive mechanism for maximizing N uptake. To date, few studies have investigated the temporal pattern and components of root exudates by Australian native plant species for BNI. This study examined root exudates from two Australian native species, Hibiscus splendens and Solanum echinatum, and contrasted with exudates of Sorghum bicolor, a plant widely demonstrated to exhibit BNI capacity. Root exudates were collected from plants at two, four, and six weeks after transplanting to solution culture. Root exudates contained three types of organic acids (OAs), oxalic, citric and succinic acids, regardless of the species. However, the two Australian natives species released larger amount of OAs in earlier development stages than S. bicolor. The total quantity of these OAs released per unit root dry mass was also seven-ten times greater for Australian native plant species compared to S. bicolor. The root exudates significantly inhibited nitrification activity over six weeks' growth in a potential nitrification assay, with S. echinatum (ca. 81% inhibition) > S. bicolor (ca. 80% inhibition) > H. splendens (ca. 78% inhibition). The narrow range of BNI capacity in the study plants limited the determination of a relationship between OAs and BNI; however, a lack of correlation between individual OAs and inhibition of nitrification suggests OAs may not directly contribute to BNI. These results indicate that Australian native species generate a strongly N conserving environment within the rhizosphere up to six weeks after germination, establishing a competitive advantage in severely N limited environments.

Ecotoxicological assessment of dewatered drinking water treatment residue for environmental recycling.

The beneficial recycle of drinking water treatment residue (DWTR) in environmental remediation has been demonstrated in many reports. However, the lack of information concerning the potential toxicity of dewatered DWTR hinders its widespread use. The present study examined the ecotoxicity of dewatered aluminum (Al) and iron (Fe) DWTR leachates to a green alga, Chlorella vulgaris. Data from the variations of cell density and chlorophyll a content suggested that algal growth in DWTR leachates was inhibited. The algal cellular oxidation stress was initially induced but completely eliminated within 72 h by antioxidant enzymes. The expression of three photosynthesis-related algae genes (psaB, psbC, and rbcL) also temporarily decreased (within 72 h). Moreover, the algal cells showed intact cytomembranes after exposure to DWTR leachates. Further investigation confirmed that inhibition of algal growth was due to DWTR-induced phosphorus (P) deficiency in growth medium, rather than potentially toxic contaminants (e.g. copper and Al) contained in DWTR. Interestingly, the leachates could potentially promote algal growth via increasing the supply of new components (e.g. calcium, kalium, magnesium, and ammonia nitrogen) from DWTR. In summary, based on the algae toxicity test, the dewatered Fe/Al DWTR was nontoxic and its environment recycling does not represent an ecotoxicological risk to algae.

Use of Fe/Al drinking water treatment residuals as amendments for enhancing the retention capacity of glyphosate in agricultural soils.

Fe/Al drinking water treatment residuals (WTRs), ubiquitous and non-hazardous by-products of drinking water purification, are cost-effective adsorbents for glyphosate. Given that repeated glyphosate applications could significantly decrease glyphosate retention by soils and that the adsorbed glyphosate is potentially mobile, high sorption capacity and stability of glyphosate in agricultural soils are needed to prevent pollution of water by glyphosate. Therefore, we investigated the feasibility of reusing Fe/Al WTR as a soil amendment to enhance the retention capacity of glyphosate in two agricultural soils. The results of batch experiments showed that the Fe/Al WTR amendment significantly enhanced the glyphosate sorption capacity of both soils (p<0.001). Up to 30% of the previously adsorbed glyphosate desorbed from the non-amended soils, and the Fe/Al WTR amendment effectively decreased the proportion of glyphosate desorbed. Fractionation analyses further demonstrated that glyphosate adsorbed to non-amended soils was primarily retained in the readily labile fraction (NaHCO3-glyphosate). The WTR amendment significantly increased the relative proportion of the moderately labile fraction (HCl-glyphosate) and concomitantly reduced that of the NaHCO3-glyphosate, hence reducing the potential for the release of soil-adsorbed glyphosate into the aqueous phase. Furthermore, Fe/Al WTR amendment minimized the inhibitory effect of increasing solution pH on glyphosate sorption by soils and mitigated the effects of increasing solution ionic strength. The present results indicate that Fe/Al WTR is suitable for use as a soil amendment to prevent glyphosate pollution of aquatic ecosystems by enhancing the glyphosate retention capacity in soils.

Comparison of metals extractability from Al/Fe-based drinking water treatment residuals.

Recycling of drinking water treatment residuals (WTRs) as environment amendments has attracted substantial interest due to their productive reuse concomitant with waste minimization. In the present study, the extractability of metals within six Al/Fe-hydroxide-comprised WTRs collected throughout China was investigated using fractionation, in vitro digestion and the toxicity characteristic leaching procedure (TCLP). The results suggested that the major components and structure of the WTRs investigated were similar. The WTRs were enriched in Al, Fe, Ca, and Mg, also contained varying quantities of As, Ba, Be, Cd, Co, Cr, Cu, K, Mn, Mo, Na, Ni, Pb, Sr, V, and Zn, but Ag, Hg, Sb, and Se were not detected. Most of the metals within the WTRs were largely non-extractable using the European Community Bureau of Reference (BCR) procedure, but many metals exhibited high bioaccessibility based on in vitro digestion. However, the WTRs could be classified as non-hazardous according to the TCLP assessment method used by the US Environmental Protection Agency (USEPA). Further analysis showed the communication factor, which is calculated as the ratio of total extractable metal by BCR procedure to the total metal, for most metals in the six WTRs, was similar, whereas the factor for Ba, Mn, Sr, and Zn varied substantially. Moreover, metals in the WTRs investigated had different risk assessment code. In summary, recycling of WTRs is subject to regulation based on assessment of risk due to metals prior to practical application.

Geochemical and ecotoxicological assessment of iron- and steel-making slags for potential use in environmental applications.

Prior to the productive use of iron- and steel-making slags as environmental amendments, a risk assessment supported by material characterization concomitant with leaching and ecotoxicological testing is necessary. Five iron- and steel-making slags were characterized geochemically, and the leachability of their elemental constituents was assessed. The toxicity of slag leachate to microalgae (Chlorella sp.), cladocerans (Ceriodaphnia dubia), and bacteria (Vibrio fischeri) was related to elemental composition. Slag leachates with the highest concentrations of dissolved elements were the most toxic (10% effective concentration [EC10] ∼1%), whereas those with the lowest concentrations of elements were the least toxic (EC10 63-85%). It was not possible to determine which elements caused the observed toxicity; however, comparisons with contaminant guidelines and published toxicity data identified several elements of potential environmental concern. Low to moderate activities were measured for radionuclides in the U and Th decay chains in slags. Based on these data, some of the slags examined herein are potentially suitable for use as environmental amendments following ≥10 times dilution to ameliorate potential toxic effects because of leachate pH.

Feasibility of using drinking water treatment residuals as a novel chlorpyrifos adsorbent.

Recent efforts have increasingly focused on the development of low-cost adsorbents for pesticide retention. In this work, the novel reuse of drinking water treatment residuals (WTRs), a nonhazardous ubiquitous byproduct, as an adsorbent for chlorpyrifos was investigated. Results showed that the kinetics and isothermal processes of chlorpyrifos sorption to WTRs were better described by a pseudo-second-order model and by the Freundlich equation, respectively. Moreover, compared with paddy soil and other documented absorbents, the WTRs exhibited a greater affinity for chlorpyrifos (log Koc = 4.76-4.90) and a higher chlorpyrifos sorption capacity (KF = 5967 mg(1-n)·L·kg(-1)) owing to the character and high content of organic matter. Further investigation demonstrated that the pH had a slight but statistically insignificant effect on chlorpyrifos sorption to WTRs; solution ionic strength and the presence of low molecular weight organic acids both resulted in concentration-dependent inhibition effects. Overall, these results confirmed the feasibility of using WTRs as a novel chlorpyrifos adsorbent.

Environmental toxicity and radioactivity assessment of a titanium-processing residue with potential for environmental use.

Thorough examination of the physicochemical characteristics of a Ti-processing residue was undertaken, including mineralogical, geochemical, and radiochemical characterization, and an investigation of the environmental toxicity of soft-water leachate generated from the residue. Concentrations of most metals measured in the leachate were low; thus, the residue is unlikely to leach high levels of potentially toxic elements on exposure to low-ionic strength natural waters. Relative to stringent ecosystem health-based guidelines, only chromium concentrations in the leachate exceeded guideline concentrations for 95% species protection; however, sulfate was present at concentrations known to cause toxicity. It is likely that the high concentration of calcium and extreme water hardness of the leachate reduced the bioavailability of some elements. Geochemical modeling of the leachate indicated that calcium and sulfate concentrations were largely controlled by gypsum mineral dissolution. The leachate was not toxic to the microalga Chlorella sp., the cladoceran Ceriodaphnia dubia, or the estuarine bacterium Vibrio fischeri. The Ti-processing residue exhibited an absorbed dose rate of 186 nGy/h, equivalent to an annual dose of 1.63 mGy and an annual effective dose of 0.326 mGy. In summary, the results indicate that the Ti-processing residue examined is suitable for productive use as an environmental amendment following 10 to 100 times dilution to ameliorate potential toxic effects due to chromium or sulfate.

Nutrient and dissolved organic carbon removal from natural waters using industrial by-products.

Attenuation of excess nutrients in wastewater and stormwater is required to safeguard aquatic ecosystems. The use of low-cost, mineral-based industrial by-products with high Ca, Mg, Fe or Al content as a solid phase in constructed wetlands potentially offers a cost-effective wastewater treatment option in areas without centralised water treatment facilities. Our objective was to investigate use of water treatment residuals (WTRs), coal fly ash (CFA), and granular activated carbon (GAC) from biomass combustion in in-situ water treatment schemes to manage dissolved organic carbon (DOC) and nutrients. Both CaO- and CaCO(3)-based WTRs effectively attenuated inorganic N species but exhibited little capacity for organic N removal. The CaO-based WTR demonstrated effective attenuation of DOC and P in column trials, and a high capacity for P sorption in batch experiments. Granular activated carbon proved effective for DOC and dissolved organic nitrogen (DON) removal in column trials, but was ineffective for P attenuation. Only CFA demonstrated effective removal of a broad suite of inorganic and organic nutrients and DOC; however, Se concentrations in column effluents exceeded Australian and New Zealand water quality guideline values. Water treated by filtering through the CaO-based WTR exhibited nutrient ratios characteristic of potential P-limitation with no potential N- or Si-limitation respective to growth of aquatic biota, indicating that treatment of nutrient-rich water using the CaO-based WTR may result in conditions less favourable for cyanobacterial growth and more favourable for growth of diatoms. Results show that selected industrial by-products may mitigate eutrophication through targeted use in nutrient intervention schemes.

Sorption of pesticides by a mineral sand mining by-product, neutralised used acid (NUA).

This study investigated the sorption-desorption behaviour of four pesticides by a by-product from mineral sand mining, commonly referred to as neutralised used acid (NUA). In batch studies the average amount of pesticide removed after 6h was 69% for atrazine, 89% for diuron, 61% for 2,4-D and 83% for chlorpyrifos. The lower sorption of 2,4-D to NUA compared with the other pesticides studied is most likely to be due to the high pH of the solutions (7.8 to 8.8) which would have resulted in 2,4-D being predominantly in an anionic form. The presence of other pesticides only significantly decreased the amount of 2,4-D sorbed from 59% to 34% when present in a mixture. Little (2 to 17%) diuron, chlorpyrifos, atrazine or 2,4-D were found to desorb from the NUA. The presence of nitrate or phosphate had minimal effect on the amount of diuron or atrazine sorbed to the NUA. However, all phosphate and nitrate treatments significantly (P<0.05) decreased the amount of 2,4-D sorbed (<50%) compared with when 2,4-D was present alone (65%). This study has shown that NUA has potential to be used as a sorbent for pesticides.

Nutrient and dissolved organic carbon removal from water using mining and metallurgical by-products.

Excess nutrient input to water bodies frequently results in algal blooms and development of oxygen deficient conditions. Mining or metallurgical by-products can potentially be utilised as filtration media within water treatment systems such as constructed wetlands, permeable reactive barriers, or drain liners. These materials may offer a cost-effective solution for the removal of nutrients and dissolved organic carbon (DOC) from natural waters. This study investigated steel-making, alumina refining (red mud and red sand) and heavy mineral processing by-products, as well as the low-cost mineral-based material calcined magnesia, in laboratory column trials. Influent water and column effluents were analysed for pH and flow rate, alkalinity, nutrient species and DOC, and a range of major cations and anions. In general, by-products with high Ca or Mg, and to a lesser extent those with high Fe content, were well-suited to nutrient and DOC removal from water. Of the individual materials examined, the heavy mineral processing residue neutralised used acid (NUA) exhibited the highest sorption capacity for P, and removed the greatest proportions of all N species and DOC from influent water. In general, NUA and mixtures containing NUA, particularly those with calcined magnesia or red mud/red sand were the most effective in removing nutrients and DOC from influent water. Post-treatment effluents from columns containing NUA and NUA/steel-making by-product, NUA/red sand and NUA/calcined magnesia mixtures exhibited large reductions in DOC, P and N concentrations and exhibited a shift in nutrient ratios away from potential N- and Si-limitation and towards potential P-limitation. If employed as part of a large-scale water treatment scheme, use of these mining and metallurgical by-products for nutrient removal could result in reduced algal biomass and improved water quality. Identification and effective implementation of mining by-products or blends thereof in constructed wetlands or other intervention structures to augment nutrient and DOC retention has considerable potential as an aquatic ecosystem management tool.

Cobalt distribution and speciation: effect of aging, intermittent submergence, in situ rice roots.

The speciation and distribution of Co in soils is poorly understood. This study was conducted using x-ray absorption spectroscopy (XAS) techniques to examine the influence of soluble cobalt in the +2 oxidation state (Co[II]) aging, submergence-dried cycling, and the presence of in vivo rice roots on the speciation and distribution of added Co(II) in soils. In the aging and submerged-dried cycling studies, Co was found to be associated with Mn oxide fraction (23 to 100% of total Co) and Fe oxide fractions (0 to 77% of total Co) of the soils as either Co(II) species or a mixed Co(II), and Co in the +3 oxidation state (Co[III]) species. The surface speciation of Co in the Mn oxide fraction suggests an innersphere complex was present and the speciation of Co in the Fe oxide fraction was an innersphere surface complex. The in vivo root box experiments showed similar Co speciation in the Mn oxide fraction (13 to 76% of total Co) as the aging and submerged-dried cycling studies. However, the Fe oxide fraction of the soil was unimportant in Co retention. A significant amount (24 to 87% of total Co) of the Co in root box treatments was identified as a Co precipitate. The importance of this finding is that in the presence of rice roots, the Co is redistributed to a Co precipitate. This work confirmed earlier macroscopic work that Mn oxides are important in the sequestration of Co in soils and the influence of roots needs to be taken into account when addressing Co speciation. The information gained from this study will be used to improve models to predict the lability and hence the availability of Co in terrestrial environments.

Aging effects on cobalt availability in soils.

Aging processes in soils can significantly affect the potential biological availability of introduced metals via incorporation into crystal lattices, diffusion into micropores, or formation of metal precipitates on the surfaces of soil minerals. Over time, metals in contact with the soil solid phase are less freely exchangeable with the soil solution and, hence, less available to soil biota. In the present study, the effects of aging on the fate and behavior of added divalent cobalt (Co2+) in a range of soils with varying physicochemical characteristics was assessed using isotope-exchange techniques, chemical extraction, and plant growth. Following addition to soil, the Co2+ salt rapidly partitioned to the soil solid phase. Particularly in soils with neutral to alkaline pH, a large percentage of the surface-bound Co was fixed in forms no longer in equilibrium with soil solution cobalt through aging reactions. Using techniques commonly applied to estimate metal bioavailability in soil, the lability (E values), plant availability (L values), and extractability of added Co2+ salts with the mild chemical extractants calcium chloride (CaCl2) and ammonium nitrate (NH4NO3) were observed to markedly decrease with time, particularly in soils with high pH or those containing appreciable quantities of iron/ manganese oxyhydroxide minerals. Results indicated rapid partitioning of added Co2+ into isotopically nonexchangeable pools, with more than 60% of the aging occurring within 15 d in most soils. Soil pH was the primary factor controlling the rate of cobalt aging and extent of exchangeability in the soils examined. Understanding the influence of long-term aging on cobalt availability in soils is necessary to accurately assess the potential risk associated with cobalt contamination of soil environments.

A predictive model of the effects of aging on cobalt fate and behavior in soil.

Metal toxicity to terrestrial organisms is influenced by a number of factors including the organisms affected and ecotoxicological end points, soil properties, aging processes, and metal speciation. The toxicity of metals added to soils can change over time through aging processes, which may reduce availability of metals via diffusion into micropores, incorporation into crystal lattices, or Ostwald ripening of precipitates. Metals which have been in contact with soil for longer periods are less able to exchange with the soil solution, rendering them less available to soil biota. The objective of this work was to investigate and model the effects of long-term aging on cobalt(II) (Co2+) (isotopic) exchangeability and potential bioavailability in a wide range of soils, as this is the form of Co commonly used in ecotoxicological investigations. After addition to soil, added soluble Co(II) rapidly partitioned to the soil solid phase, and in alkaline soils a large percentage of this surface-bound Co was fixed through aging reactions in forms that were no longer in equilibrium with the soil solution Co. Analyses indicated that soil pH and incubation time were the most important factors affecting Co(II) aging. The rate and extent of aging of added Co(II) could be accurately predicted across all soils using a semi-mechanistic model that suggested Co was fixed through reactions that we postulate were related to surface oxidation/precipitation/nucleation as driven by hydrolysis reactions at the surface of soil minerals.

A novel technique to determine cobalt exchangeability in soils using isotope dilution.

The environmental risk posed by Co contamination is largely a function of its oxidation state. Our objective was to assess the potential biological availability of Co and the reactions and fate of soluble Co(II) after addition to soils with varying physical and chemical characteristics. A potential risk in quantifying exchangeable Co in soils using isotope dilution techniques is the possible presence of two species of Co in soil solution and adsorbed on soil solid phases [Co(II) and Co(III)], coupled with the possibility that when an isotope of Co is added it may undergo a change in oxidation state during the measurement phase. In this study, we have utilized an isotope dilution technique with cation exchange and high-performance liquid chromatography-inductively coupled plasma-mass spectrometry to determine the isotopically exchangeable Co fraction in several soils with varying characteristics such as differing Al, Fe, and Mn oxide content; pH; and organic carbon content. The application of the cation exchange procedure adjusts measurements of isotopically exchangeable Co to correct for the presence of non-exchangeable 57Co not in equilibrium with the solution phase. Results indicated that oxidation of added 57Co(II) to 57Co(III) or precipitation of 57Co(II) may occur on the surfaces of some soils, particularly those with a high pH or substantial quantities of Mn oxide minerals. No detectable Co(III)(aq) was found in the aqueous extracts of the soils examined.

Cesium desorption from illite as affected by exudates from rhizosphere bacteria.

Biogeochemical processes in the rhizosphere can significantly alter interactions between contaminants and soil minerals. In this study, several strains of bacteria that exude aluminum (Al)-chelating compounds were isolated from the rhizosphere of crested wheatgrass (Agropyron desertorum) collected from the Idaho National Laboratory (INL). We examined the effects of exudates from bacteria in the genera Bacillus, Ralstonia, and Enterobacter on cesium (Cs) desorption from illite. Exudates from these strains of bacteria significantly enhanced Cs desorption from illite. In addition, Cs desorption increased with increasing Bacillus exudate concentrations. Cesium desorption from illite as a function of both exudate type and concentration was positively correlated with Al dissolution, suggesting that the Al-complexing ability of the exudates played an important role in enhancing Cs desorption. The density of frayed edge sites (FES) on illite increased as a result of treatment with bacterial exudates, while the Cs/K selectivity of FES decreased. These results suggestthat exudates from bacteria isolated from the rhizosphere can enhance Cs desorption from frayed edges of illite and, therefore, can alter Cs availability in micaceous soils.