Understanding the nature of atmospheric acid processing of mineral dusts in supplying bioavailable phosphorus to the oceans.

Acidification of airborne dust particles can dramatically increase the amount of bioavailable phosphorus (P) deposited on the surface ocean. Experiments were conducted to simulate atmospheric processes and determine the dissolution behavior of P compounds in dust and dust precursor soils. Acid dissolution occurs rapidly (seconds to minutes) and is controlled by the amount of H+ ions present. For H+ < 10-4 mol/g of dust, 1-10% of the total P is dissolved, largely as a result of dissolution of surface-bound forms. At H+ > 10-4 mol/g of dust, the amount of P (and calcium) released has a direct proportionality to the amount of H+ consumed until all inorganic P minerals are exhausted and the final pH remains acidic. Once dissolved, P will stay in solution due to slow precipitation kinetics. Dissolution of apatite-P (Ap-P), the major mineral phase in dust (79-96%), occurs whether calcium carbonate (calcite) is present or not, although the increase in dissolved P is greater if calcite is absent or if the particles are externally mixed. The system was modeled adequately as a simple mixture of Ap-P and calcite. P dissolves readily by acid processes in the atmosphere in contrast to iron, which dissolves more slowly and is subject to reprecipitation at cloud water pH. We show that acidification can increase bioavailable P deposition over large areas of the globe, and may explain much of the previously observed patterns of variability in leachable P in oceanic areas where primary productivity is limited by this nutrient (e.g., Mediterranean).

Enhanced Phosphorus Locking by Novel Lanthanum/Aluminum-Hydroxide Composite: Implications for Eutrophication Control.

Lanthanum (La) bearing materials have been widely used to remove phosphorus (P) in water treatment. However, it remains a challenge to enhance phosphate (PO4) adsorption capacity and La usage efficiency. In this study, La was coprecipitated with aluminum (Al) to obtain a La/Al-hydroxide composite (LAH) for P adsorption. The maximum PO4 adsorption capacities of LAH (5.3% La) were 76.3 and 45.3 mg P g-1 at pH 4.0 and 8.5, which were 8.5 and 5.3 times higher than those of commercially available La-modified bentonite (Phoslock, 5.6% La), respectively. P K-edge X-ray absorption near edge structure analysis showed that PO4 was preferentially bonded with Al under weakly acid conditions (pH 4.0), while tended to associate with La under alkaline conditions (pH 8.5). La LIII-edge extended X-ray absorption fine structure analysis indicated that PO4 was bonded on La sites by forming inner sphere bidentate-binuclear complexes and oxygen defects exhibited on LAH surfaces, which could be active adsorption sites for PO4. The electrostatic interaction, ligand exchange, and oxygen defects on LAH surfaces jointly facilitated PO4 adsorption but with varied contribution under different pH conditions. The combined contribution of two-component of La and Al may be an important direction for the next generation of commercial products for eutrophication mitigation.

Mechanism of Vanadium Leaching during Surface Weathering of Basic Oxygen Furnace Steel Slag Blocks: A Microfocus X-ray Absorption Spectroscopy and Electron Microscopy Study.

Basic oxygen furnace (BOF) steelmaking slag is enriched in potentially toxic V which may become mobilized in high pH leachate during weathering. BOF slag was weathered under aerated and air-excluded conditions for 6 months prior to SEM/EDS and µXANES analysis to determine V host phases and speciation in both primary and secondary phases. Leached blocks show development of an altered region in which free lime and dicalcium silicate phases were absent and Ca-Si-H was precipitated (CaCO3 was also present under aerated conditions). µXANES analyses show that V was released to solution as V(V) during dicalcium silicate dissolution and some V was incorporated into neo-formed Ca-Si-H. Higher V concentrations were observed in leachate under aerated conditions than in the air-excluded leaching experiment. Aqueous V concentrations were controlled by Ca3(VO4)2 solubility, which demonstrate an inverse relationship between Ca and V concentrations. Under air-excluded conditions Ca concentrations were controlled by dicalcium silicate dissolution and Ca-Si-H precipitation, leading to relatively high Ca and correspondingly low V concentrations. Formation of CaCO3 under aerated conditions provided a sink for aqueous Ca, allowing higher V concentrations limited by kinetic dissolution rates of dicalcium silicate. Thus, V release may be slowed by the precipitation of secondary phases in the altered region, improving the prospects for slag reuse.

Identification and Quantification of Nitrogen in a Reservoir, Jiaodong Peninsula, China.

Identification of nitrogen (N) sources is important in water quality control and management. Nitrogen pollution can lead to eutrophication of waterbodies and high concentrations of nitrate in drinking water can pose potential health problems. The 15N isotope and nitrogen fluxes budget approach is useful for determining the source of to surface waters. In this study, mass balance and 15N isotope approaches and nitrogen flux budgets were applied to identify total nitrogen (TN) sources and nitrogen transformation processes in the Menlou Reservoir (MR), Jiaodong Peninsula, China. The different fractions of nitrogen and their 15N isotope signatures were analyzed in the reservoir water, river water, groundwater, soil, and atmospheric precipitation. The results indicate that surface runoff pollution (e.g., fertilizer and animal manure) is the main source of in MR. High concentrations of TN in MR are caused by low nitrogen self-purification (denitrification) rate, low sediment adsorption capacity, and the influx of rich groundwater.

Effect of Ocean Acidification on Organic and Inorganic Speciation of Trace Metals.

Rising concentrations of atmospheric carbon dioxide are causing acidification of the oceans. This results in changes to the concentrations of key chemical species such as hydroxide, carbonate and bicarbonate ions. These changes will affect the distribution of different forms of trace metals. Using IPCC data for pCO2 and pH under four future emissions scenarios (to the year 2100) we use a chemical speciation model to predict changes in the distribution of organic and inorganic forms of trace metals. Under a scenario where emissions peak after the year 2100, predicted free ion Al, Fe, Cu, and Pb concentrations increase by factors of up to approximately 21, 2.4, 1.5, and 2.0 respectively. Concentrations of organically complexed metal typically have a lower sensitivity to ocean acidification induced changes. Concentrations of organically complexed Mn, Cu, Zn, and Cd fall by up to 10%, while those of organically complexed Fe, Co, and Ni rise by up to 14%. Although modest, these changes may have significance for the biological availability of metals given the close adaptation of marine microorganisms to their environment.

Use of bauxite residue (red mud) as a low cost sorbent for sulfide removal in polluted water remediation.

Sulfide is an important pollutant in aqueous systems. Sulfide removal from polluted waters is required prior to discharge. Red mud (RM) is a solid waste of bauxite processing that is rich in reactive iron oxides and consequently has the potential to be used to remove sulfide from aqueous systems. A series of experiments was undertaken using raw and sintered RM to remove sulfide from waters. RM was highly efficient at sulfide removal (average 75% sulfide removal at initial concentration of ∼5 mg L(-1), with 500 mg L(-1) RM addition) due to both physical adsorption (high specific area) and chemical reaction (with amorphous Fe). Sintered RM, which has a lower surface area and lower mineral reactivity, was much less efficient at removing sulfide (∼20% removal under equivalent experimental conditions). Furthermore, concomitant metal release from raw RM was lower than for sintered RM during the sulfide removal process. The results showed that raw RM is a potentially suitable material for sulfide removal from polluted waters and consequently could be used as a low cost alternative treatment in certain engineering applications.

Field method for preservation of total mercury in waters, including those associated with artisanal scale gold mining.

Analysis of mercury (Hg) in natural water samples has routinely been impractical in many environments, for example, artisanal and small-scale gold mines (ASGM), where difficult conditions make monitoring of harmful elements and chemicals used in the processes highly challenging. Current sampling methods require the use of hazardous or expensive materials, and so difficulties in sample collection and transport are elevated. To solve this problem, a solid-phase extraction-based method was developed for the sampling and preservation of dissolved Hg in natural water samples, particularly those found around ASGM sites. Recoveries of 85% ± 10% total Hg were obtained during 4 weeks of storage in refrigerated (4 °C, dark) and unrefrigerated (16 °C, dark) conditions, and from a representative river water spiked to 1 µg L-1 Hg2+, 94% ± 1% Hg recovery was obtained. Solid-phase extraction loading flow rates were tested at 2, 5, and 10 mL min-1 with no breakthrough of Hg, and sorbent stability showed no breakthrough of Hg up to 2 weeks after functionalisation. The method was deployed across five artisanal gold mines in Kakamega gold belt, Kenya, to assess Hg concentrations in mine shaft water, ore washing ponds, and river and stream water, including drinking water sources. In all waters, Hg concentrations were below the WHO guideline limit value of 6 µg L-1, but drinking water sources contained trace concentrations of up to 0.35 µg L-1 total Hg, which may result in negative health effects from long-term exposure. The SPE method developed and deployed here is a robust sampling method that can therefore be applied in future Hg monitoring, toxicology, and environmental work to provide improved data that is representative of total dissolved Hg in water samples.

Impact of suspended inorganic particles on phosphorus cycling in the Yellow River (China).

Phosphorus (P) in water and sediment in the Yellow River was measured for 21 stations from the source to the Bohai Sea in 2006-2007. The average total particulate matter (TPM) increased from 40 mg/L (upper reaches) to 520 mg/L (middle reaches) and 950 mg/L in the lower reaches of the river. The average dissolved PO4 concentration (0.43 µmol/L) was significantly higher than that in 1980's but lower than the world average level despite high nutrient input to the system. Much of the P input was removed by adsorption, which was due to the high TPM rather than the surface activity of the particles since they had low labile Fe and low affinity for P. The sediment was a sink for P in the middle to lower reaches but not in the upper to middle reaches. TPM has been reduced by more than an order of magnitude due to artificial dams operating over recent decades. Modeling revealed that TPM of 0.2-1 g/L was a critical threshold for the Yellow River, below which most of the phosphate input cannot be removed by the particles and may cause eutrophication. These findings are important for river management and land-ocean modeling of global biogeochemical P cycling.

Behavior of aluminum, arsenic, and vanadium during the neutralization of red mud leachate by HCl, gypsum, or seawater.

Red mud leachate (pH 13) collected from Ajka, Hungary is neutralized to < pH 10 by HCl, gypsum, or seawater addition. During acid neutralization >99% Al is removed from solution during the formation of an amorphous boehmite-like precipitate and dawsonite. Minor amounts of As (24%) are also removed from solution via surface adsorption of As onto the Al oxyhydroxides. Gypsum addition to red mud leachate results in the precipitation of calcite, both in experiments and in field samples recovered from rivers treated with gypsum after the October 2010 red mud spill. Calcite precipitation results in 86% Al and 81% As removal from solution, and both are nonexchangeable with 0.1 mol L(-1) phosphate solution. Contrary to As associated with neoformed Al oxyhydroxides, EXAFS analysis of the calcite precipitates revealed only isolated arsenate tetrahedra with no evidence for surface adsorption or incorporation into the calcite structure, possibly as a result of very rapid As scavenging by the calcite precipitate. Seawater neutralization also resulted in carbonate precipitation, with >99% Al and 74% As removed from solution during the formation of a poorly ordered hydrotalcite phase and via surface adsorption to the neoformed precipitates, respectively. Half the bound As could be remobilized by phosphate addition, indicating that As was weakly bound, possibly in the hydrotalcite interlayer. Only 5-16% V was removed from solution during neutralization, demonstrating a lack of interaction with any of the neoformed precipitates. High V concentrations are therefore likely to be an intractable problem during the treatment of red mud leachates.

Gypsum addition to soils contaminated by red mud: implications for aluminium, arsenic, molybdenum and vanadium solubility.

Red mud is highly alkaline (pH 13), saline and can contain elevated concentrations of several potentially toxic elements (e.g. Al, As, Mo and V). Release of up to 1 million m(3) of bauxite residue (red mud) suspension from the Ajka repository, western Hungary, caused large-scale contamination of downstream rivers and floodplains. There is now concern about the potential leaching of toxic metal(loid)s from the red mud as some have enhanced solubility at high pH. This study investigated the impact of red mud addition to three different Hungarian soils with respect to trace element solubility and soil geochemistry. The effectiveness of gypsum amendment for the rehabilitation of red mud-contaminated soils was also examined. Red mud addition to soils caused a pH increase, proportional to red mud addition, of up to 4 pH units (e.g. pH 7 â†’ 11). Increasing red mud addition also led to significant increases in salinity, dissolved organic carbon and aqueous trace element concentrations. However, the response was highly soil specific and one of the soils tested buffered pH to around pH 8.5 even with the highest red mud loading tested (33 % w/w); experiments using this soil also had much lower aqueous Al, As and V concentrations. Gypsum addition to soil/red mud mixtures, even at relatively low concentrations (1 % w/w), was sufficient to buffer experimental pH to 7.5-8.5. This effect was attributed to the reaction of Ca(2+) supplied by the gypsum with OH(-) and carbonate from the red mud to precipitate calcite. The lowered pH enhanced trace element sorption and largely inhibited the release of Al, As and V. Mo concentrations, however, were largely unaffected by gypsum induced pH buffering due to the greater solubility of Mo (as molybdate) at circumneutral pH. Gypsum addition also leads to significantly higher porewater salinities, and column experiments demonstrated that this increase in total dissolved solids persisted even after 25 pore volume replacements. Gypsum addition could therefore provide a cheaper alternative to recovery (dig and dump) for the treatment of red mud-affected soils. The observed inhibition of trace metal release within red mud-affected soils was relatively insensitive to either the percentage of red mud or gypsum present, making the treatment easy to apply. However, there is risk that over-application of gypsum could lead to detrimental long-term increases in soil salinity.

Nanobubble aeration enhanced wastewater treatment and bioenergy generation in constructed wetlands coupled with microbial fuel cells.

Artificial aeration is a widely used approach in wastewater treatment to enhance the removal of pollutants, however, traditional aeration techniques have been challenging due to the low oxygen transfer rate (OTR). Nanobubble aeration has emerged as a promising technology that utilise nano-scale bubbles to achieve higher OTRs owing to their large surface area and unique properties such as longevity and reactive oxygen species generation. This study, for the first time, investigated the feasibility of coupling nanobubble technology with constructed wetlands (CWs) for treating livestock wastewater. The results demonstrated that nanobubble-aerated CWs achieved significantly higher removal efficiencies of total organic carbon (TOC) and ammonia (NH4+-N), at 49 % and 65 %, respectively, compared to traditional aeration treatment (36 % and 48 %) and the control group (27 % and 22 %). The enhanced performance of the nanobubble-aerated CWs can be attributed to the nearly three times higher amount of nanobubbles (Ø < 1 µm) generated from the nanobubble pump (3.68 × 108 particles/mL) compared to the normal aeration pump. Moreover, the microbial fuel cells (MFCs) embedded in the nanobubble-aerated CWs harvested 5.5 times higher electricity energy (29 mW/m2) compared to the other groups. The results suggested that nanobubble technology has the potential to trigger the innovation of CWs by enhancing their capacity for water treatment and energy recovery. Further research needs are proposed to optimise the generation of nanobubbles, allowing them to be effectively coupled with different technologies for engineering implementation.

Controlling internal nitrogen and phosphorus loading using Ca-poor soil capping in shallow eutrophic lakes: Long-term effects and mechanisms.

Clean soil is a potential capping material for controlling internal nutrient loading and helping the recovery of macrophytes in eutrophic lakes, but the long-term effects and underlying mechanisms of clean soil capping under in-situ conditions remain poorly understood. In this study, a three-year field capping enclosure experiment combining intact sediment core incubation, in-situ porewater sampling, isotherm adsorption experiments and analysis of sediment nitrogen (N) and phosphorus (P) fractions was conducted to assess the long-term performance of clean soil capping on internal loading in Lake Taihu. Our results indicate that clean soil has excellent P adsorption and retention capacity as an ecologically safe capping material and can effectively mitigate NH4+-N and SRP (soluble reactive P) fluxes at the sediment-water interface (SWI) and porewater SRP concentration for one year after capping. The mean NH4+-N and SRP fluxes of capping sediment were 34.86 mg m-2 h-1 and -1.58 mg m-2 h-1, compared 82.99 mg m-2 h-1 and 6.29 mg m-2 h-1 for control sediment. Clean soil controls internal NH4+-N release through cation (mainly Al3+) exchange mechanisms, while for SRP, clean soil can not only react with SRP due to its high Al and Fe content, but also stimulate the migration of active Ca2+ to the capping layer, thus precipitating as Ca-bound P (Ca-P). Clean soil capping also contributed to the restoration of macrophytes during the growing season. However, the effect of controlling internal nutrient loading only lasted for one year under in-situ conditions, after which the sediment properties returned to pre-capping conditions. Our results highlight that clean Ca-poor soil is a promising capping material and further research is needed to extend the longevity of this geoengineering technology.

Horizontal transmission of Thelohania contejeani in the endangered white-clawed (Austropotamobius pallipes) and the invasive signal crayfish (Pacifastacus leniusculus).

The microsporidian parasite Thelohania contejeani causes porcelain disease and has been implicated in mass mortalities in populations of the endangered European crayfish Austropotamobius pallipes. However, the route of parasite transmission is not known. This paper investigates the horizontal transmission of T. contejeani between A. pallipes hosts as well as its transmissibility to the invasive signal crayfish (Pacifastacus leniusculus). Field collected juvenile A. pallipes and P. leniusculus were assigned to 1 of 3 experimental treatments; fed heavily infected A. pallipes tissue, exposed to water from tanks housing heavily parasitized A. pallipes, and a control group to provide an estimate of the baseline infection levels in the field. After 26 weeks, abdominal muscle samples were screened by PCR for T. contejeani. Infection was significantly higher in the treatment groups (83% in the cannibalism treatment, 42% in the water exposure treatment) than in the control group (4%), providing evidence for horizontal transmission of the parasite between A. pallipes hosts. Cannibalism and scavenging are common amongst crayfish, providing transmission opportunities in the field. The study also provides the first direct evidence for transmission of the parasite from an indigenous European crayfish species to the invasive signal crayfish, with 50% of P. leniusculus in each treatment, and 8% of control animals infected. We discuss the possibility that high density populations of the invasive signal crayfish may serve either as reservoirs or sinks for the parasite.

Studies on synthesis and characteristics of zeolite prepared from Indian fly ash.

In the present study, samples of coal fly ash were obtained from seven major Indian thermal power plants. These samples were transformed into fly ash zeolite (FAZ) using hydrothermal activation by treatment with NaOH. All experiments were carried out at 100 degrees C, but with different solid:liquid ratios, different concentrations of alkali and different incubation times. The chemical composition, mineralogy and morphology of the fly ash and FAZ were determined by wet chemical method after Na2CO3 fusion, x-ray diffraction and scanning electron microscopy. The cation exchange capacity of fly ash and FAZ was determined using the ammonium acetate method (IS:2720). The ammonium exchange capacity was determined by the titrimetric method. The experiments demonstrate that zeolite can be synthesized at 100 degrees C using alkali. The cation exchange capacity and ammonium adsorption capacity of FAZ (up to 250 meq/100 g and 22.93 mg NH4+/g respectively) indicate that the FAZ may be potentially useful to reduce heavy metals and other pollutants from contaminated environments. Therefore, zeolitization at low temperature potentially allows waste fly ash to be used in an economically advantageous way.

Utilization of coal fly ash waste for effective recapture of phosphorus from waters.

Reutilization of the waste by-products from industrial and agricultural activities is crucially important towards attainment of environmental sustainability and the 'circular economy'. In this study, we have developed and evaluated a sustainably-sourced adsorbent from coal fly ash, which was modified by a small amount of lanthanum (La-FA), for the recapture of phosphorous (P) from both synthetic and real natural waters. The prepared La-FA adsorbent possessed typical characteristic diffraction peaks similar to zeolite type Na-P1, and the BET surface area of La-FA was measured to be 10.9 times higher than that of the original FA. Investigation of P adsorption capability indicated that the maximum adsorption (10.8 mg P g-1) was 6.14 times higher than that (1.8 mg P g-1) of the original fly ash material. The ζ potentials measurement and P K-edge X-ray Absorption Near Edge Structure (XANES) spectra demonstrated that P was bonded on La-FA surfaces via an adsorption mechanism. After applying the proposed adsorbent to real lake water with La/P molar ratios in the range from 0.5:1 to 3:1, the La-FA adsorbent showed the highest phosphate removal ability with a La/P molar ratio 1:1, and the P adsorption was similar to that performance with the synthetic solution. Moreover, the La-FA absorbent produced a negligible effect on the concentrations of total dissolved nitrogen (TDN), NH4+-N and NO3--N in water. This study thus provides a potential material for effective P recapture and details of its operation.

Effects of elevated sulfate in eutrophic waters on the internal phosphate release under oxic conditions across the sediment-water interface.

Eutrophication in freshwater environments may be enhanced by the elevation of sulfate in waters, through the release of internal phosphorus (P) from anoxic sediments. However, the influence of increasing but modest sulfate concentrations (less than 3000 µM) on P release under oxic conditions across the sediment-water interface (SWI) in eutrophic freshwater is poorly understood. In this study, the profiles of P, iron (Fe), sulfur (S) and physicochemical parameters were measured in a simulated lacustrine system with varying concentrations of sulfate (970-2600 µM) in overlying water. The results indicated that elevated concentrations of sulfate increased the soluble reactive P in overlying waters under oxic conditions across the SWI. A 100 µM increase of sulfate was found to induce a 0.128 mgm-2d-1 increase of P flux from surface sediments into overlying waters under oxic conditions. Higher sulfate concentrations in the overlying waters increased the concentrations of labile S(-II) in the deep sediments, due to sulfate penetration and subsequent reduction to S(-II). We also found the fluxes of labile Fe (10.34 to 18.33 mgm-2d-1) and P (2.70 to 1.33 mgm-2d-1) from deep to surface sediment were both positive and greater than the corresponding fluxes (Fe, 2.2 to 3.51 and P, 2.6 to 0.39 mgm-2d-1, respectively) from surface sediment to the overlying water, suggesting that reduction of P-bearing Fe(III)(oxyhydr)oxides in deep anoxic sediment acted as a major source of internal P release. In addition, the upward flux of Fe(II) was significantly lower under higher sulfate conditions, indicating that the Fe(II) flux could be mitigated by formation of Fe(II) sulfides in the deep sediment. Under these conditions, less Fe(II) from deep sediments could be re-oxidized and combine with P in the surface, oxic sediment, thereby reducing the retention capacity for P and leading to higher release of internal P to the water column.

Cryogenic circulation for indoor air pollution control.

Hazardous outdoor air pollution has severely affected indoor air quality, threatening the health of billions of people. However, existing indoor air purification technologies are unsatisfactory due to some inherent limitations such as poor efficiency, limited target pollutants, the need to frequently replace filters or adsorbents, or the generation of harmful by-products. Here, we studied the effect and mechanism of cryogenic circulation for indoor air purification. Experimental results show that up to 99% of indoor PM2.5 from ambient air was removed at -18 °C. The morphological measurements indicate that micrometer-sized particles are formed concomitantly with the reduction of nanometer- or submicron-sized particles, suggesting that condensational growth of fine particles is responsible for the removal. Applying the method to gaseous pollutant purification demonstrates that 98% of NO2 is condensed and removed from the ambient air at -50 °C, implying that the method would be effective for multiple indoor pollutants with higher boiling points. Cryogenic condensation may provide a principle for continuous indoor air purification via modified air conditioners and humidifiers in cases where health benefits outweigh energy consumption concerns.

Leaching behaviour of co-disposed steel making wastes: Effects of aeration on leachate chemistry and vanadium mobilisation.

Steelmaking wastes stored in landfill, such as slag and spent refractory liners, are often enriched in toxic trace metals (including V). These may become mobile in highly alkaline leachate generated during weathering. Fresh steelmaking waste was characterised using XRD, XRF, and SEM-EDX. Batch leaching tests were performed under aerated, air-excluded and acidified conditions to determine the impact of atmospheric CO2 and acid addition on leachate chemistry. Phases commonly associated with slag including dicalcium silicate, dicalcium aluminoferrite, a wüstite-like solid solution and free lime were identified, as well as a second group of phases including periclase, corundum and graphite which are representative of refractory liners. During air-excluded leaching, dissolution of free lime and dicalcium silicate results in a high pH, high Ca leachate in which the V concentration is low due to the constraint imposed by Ca3(VO4)2 solubility limits. Under aerated conditions, carbonation lowers the leachate pH and provides a sink for aqueous Ca, allowing higher concentrations of V to accumulate. Below pH 10, leachate is dominated by periclase dissolution and secondary phases including monohydrocalcite and dolomite are precipitated. Storage of waste under saturated conditions that exclude atmospheric CO2 would therefore provide the optimal environment to minimise V leaching during weathering.