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Using phosphate rock to immobilize metals in soil and increase arsenic uptake by hyperaccumulator Pteris vittata.

This greenhouse experiment evaluated the effects of phosphate rock (PR) on arsenic and metal uptake by the arsenic hyperaccumulator Pteris vittata in a soil spiked with arsenic and heavy metals Cd, Pb and Zn. Five soil treatments were used, 1) control with no arsenic, 2) spiked with 50 mg kg(-1) As (As) as Na2H AsO4, 3) spiked with 50 mg kg(-1) As and P as PR (AsP), 4) spiked with 50 mg kg(-1) As, Pb, Cd, and Zn (AsM), and 5) spiked with 50 mg kg(-1) As, Pb, Cd, Zn and P (AsMP). The plants were harvested after growing in the soil for five weeks. Compared to the As treatment, the presence of heavy metals (AsM) reduced arsenic concentrations in the fronds from 1631 to 608 mg kg(-1). However, this effect was mitigated by PR (AsMP), with arsenic concentrations in the fronds increased from 608 to 1046 mg kg(-1). Phosphate rock also significantly reduced Pb (13.5 to 4.10 mg kg(-1)) and Cd (13.0 to 3.45 mg kg(-1)) concentrations in the fronds. Most of the arsenic in P. vittata was accumulated in the fronds (89-93%). Compared to the control, P was more concentrated in the roots along with less P being translocated to the fronds in the treatments with arsenic. While in those same treatments higher Ca concentrations in both the fronds and roots were observed. This research shows that PR was effective in increasing arsenic uptake and decreasing metal uptake by P. vittata and thus can be used as a cost-effective amendment for phytoremediation of arsenic and metal polluted soils.

Arsenic↗

Effectiveness of leaded petrol phase-out in Tianjin, China based on the aerosol lead concentration and isotope abundance ratio.

The phase-out of leaded petrol has been a measure widely used to reduce atmospheric lead pollution. Since the 1980s, China began to promote unleaded petrol. In order to assess the effectiveness of the measure an isotope fingerprint technique was applied for aerosol samples in the city of Tianjin. After dilute acid leaching, the lead concentration and isotope abundance ratios were determined for 123 samples collected in Tianjin during eight years (1994-2001). The 206Pb/207Pb ratio was lower in summer, when coal combustion emission was low and vehicle exhaust became more important, indicating that the 206Pb/207Pb ratio of leaded petrol in Tianjin is lower than that of aerosol samples. The 206Pb/207Pb ratio gradually increased from 1994 to 2001, a trend that suggests that the contribution from vehicle exhaust was diminishing. Overall, the measurements matched well with national statistical data of leaded and unleaded petrol production. After the nationwide switch to unleaded gasoline, comprehensive control measures are urgently needed to reduce air lead pollution in China, as aerosol lead reduced slightly but remains at a relatively high level.

Aerosols↗

Phosphate sources and their suitability for remediation of contaminated soils.

Phosphate minerals and specifically apatite show promise for environmental cleanup because they can form stable compounds with a wide range of cationic contaminants. However, phosphate minerals naturally accumulate some heavy metals that may cause additional contamination of the environment if used improperly. Nine commercially available phosphate materials were evaluated for remediation of contaminated soil based on solubility, concentration of metal/metalloid impurities, and leachability of impurity metal/metalloids. The phosphate materials consisted of three groups: processed (i.e., fertilizers), mined (rock phosphates from different formations), and biogenic (ground fish bone). Processed and mined rock phosphates contained relatively high total concentrations of As, Co, Cr, and Cu but did not exceed the RCRA toxicity characteristic leaching procedure (TCLP) limits. Biogenic apatite contained much lower metal concentrations than processed and mined rock phosphate and was appreciably more soluble. By combining biogenic and mined phosphate it is possible to obtain a wide range of phosphate release rates, permitting rapid immobilization of contaminants while providing a slow release of phosphate for continued long-term treatment.

Arsenic↗

The implications of integrated assessment and modelling studies for the future remediation of chromite ore processing residue disposal sites.

Chromite ore processing residue (COPR) waste from a former chromium chemical works (1830-1968) is still contaminating groundwater in Glasgow, Scotland, with carcinogenic hexavalent chromium, Cr(VI). An integrated analytical, experimental and modelling approach has identified and accounted for mineral phases and processes responsible for the retention and release of Cr(VI) under prevailing field conditions. Both the nature of mineral phase retention and the buffered high pH of the sites, however, militate against direct remediative treatment of the source material, for example by the application of generic methods (e.g. FeSO4) that have been successfully employed elsewhere for the reduction of Cr(VI) to Cr(III) in other matrices. The interception and treatment of groundwater to remove Cr(VI) and the capping of sites to reduce human exposure to airborne Cr(VI)-contaminated dust may well be more realistic and effective, at least in the short to medium term.

Chromium↗

Exogenous enzyme supplements to promote treatment efficiency in constructed wetlands.

Extracellular enzymes play a central role in the breakdown of organic pollutants. In wetlands constructed to treat wastewaters, supplementing the naturally occurring soil enzymes may result in faster pollutant removal, or breakdown of novel pollutants, but only if the added enzymes could retain their catalytic activity. In this study, the persistence of exogenous enzyme supplements was investigated. Adding cellobiohydrolase and beta-glucosidase to sterilised soil increased enzyme activity (range 375-4210%); although the increased activity began to decline after just 10-15 days. Thus, without an active microbial population, enhanced enzyme activity is unlikely to be long lived. However, with the naturally occurring soil microbes present to maintain the improved biodegradative capacity, cellobiohydrolase and beta-glucosidase additions created significant increases (range 173-530%) in activity and these persisted for more than 6 weeks. These findings therefore support the proposal that enzyme additions can enhance enzymic biodegradation processes, and suggest that this may be achieved primarily through a 'pump-priming' mechanism.

Biodegradation, Environmental↗

Abatement of mercury pollution in the small-scale gold mining industry: restructuring the policy and research agendas.

This paper critiques contemporary research and policy approaches taken toward the analysis and abatement of mercury pollution in the small-scale gold mining sector. Unmonitored releases of mercury from gold amalgamation have caused considerable environmental contamination and human health complications in rural reaches of sub-Saharan Africa, Latin America and Asia. Whilst these problems have caught the attention of the scientific community over the past 15-20 years, the research that has since been undertaken has failed to identify appropriate mitigation measures, and has done little to advance understanding of why contamination persists. Moreover, the strategies used to educate operators about the impacts of acute mercury exposure, and the technologies implemented to prevent further pollution, have been marginally effective at best. The mercury pollution problem will not be resolved until governments and donor agencies commit to carrying out research aimed at improving understanding of the dynamics of small scale gold mining communities. Acquisition of this knowledge is the key to designing and implementing appropriate support and abatement measures.

Environmental Pollutants↗

Spatial variations of mercury in sediment of Minamata Bay, Japan.

Mercury-contaminated effluent was discharged into Minamata Bay from a chemical plant over a period of approximately 40 years until 1968. In October 1977, the Minamata Bay Pollution Prevention Project was initiated to dispose of sedimentary sludge containing mercury concentrations higher than 25 mg kg(-1). In March 1990, the project was completed. In an effort to estimate current contamination in the bay, the vertical and horizontal distributions of mercury in sediment were investigated. Sediment core samples were collected on June 26, 2002 at 16 locations in Minamata Bay and Fukuro Bay located in the southern part of Minamata Bay. The sediment in Fukuro Bay had not been dredged. The total mercury concentration in surface sediment was 1.4-4.3 mg kg(-1) (2.9+/-0.9 mg kg(-1), n=9) for the dredged area of Minamata Bay and 0.3-4.8 mg kg(-1) (3.6+/-1.6 mg kg(-1), n=4) for Fukuro Bay. In the lower layers of long cores taken from both areas, the total mercury concentration decreased with depth and finally showed relatively uniform low values. These values can be considered to represent the background concentration absent of anthropogenic influence, which was estimated for the study area to be 0.068+/-0.012 mg kg(-1) (n=10). From the surface, the total mercury concentration in Fukuro Bay increased with depth and reached a maximum at 8-14 cm. In Minamata Bay, several centimeters from the surface the total mercury concentration did not change significantly having considerably higher values than the background level. At six stations, the methylmercury concentration was determined. Although the vertical variations were similar to those for total mercury, Fukuro Bay sediment showed a higher concentration of methylmercury than Minamata Bay sediment.

Environmental Monitoring↗

Comparative evaluation of short-term leach tests for heavy metal release from mineral processing waste.

Evaluation of metal leaching using a single leach test such as the Toxicity Characteristic Leaching Procedure (TCLP) is often questionable. The pH, redox potential (E(h)), particle size and contact time are critical variables in controlling metal stability, not accounted for in the TCLP. This paper compares the leaching behavior of metals in mineral processing waste via short-term extraction tests such as TCLP, Field Leach Test (FLT) used by USGS and deionized water extraction tests. Variation in the extracted amounts was attributed to the use of different particle sizes, extraction fluid and contact time. In the controlled pH experiments, maximum metal extraction was obtained at acidic pH for cationic heavy metals such as Cu, Pb and Zn, while desorption of Se from the waste resulted in high extract concentrations in the alkaline region. Precipitation of iron, caused by a pH increase, probably resulted in co-precipitation and immobilization of Cu, Pb and Zn in the alkaline pH region. A sequential extraction procedure was performed on the original waste and the solid residue from the E(h)-pH experiments to determine the chemical speciation and distribution of the heavy metals. In the as-received waste, Cu existed predominantly in water soluble or sulfidic phases, with no binding to carbonates or iron oxides. Similar characteristics were observed for Pb and Zn, while Se existed mostly associated with iron oxides or sulfides. Adsorption/co-precipitation of Cu, Se and Pb on precipitated iron hydroxides was observed in the experimental solid residues, resulting in metal immobilization above pH 7.

Hydrogen-Ion Concentration↗

Three new arsenic hyperaccumulating ferns.

Phytoremediation, an emerging, plant-based technology for the removal of toxic contaminants from soil and water, has been receiving increased attention. The prerequisite for successful phytoremediation is the existence of hyperaccumulator plants. Designed to search for new arsenic (As) hyperaccumulators, an experiment was conducted under greenhouse conditions in a completely randomized design with four replications. This experiment identified Pteris biaurita L., P. quadriaurita Retz and P. ryukyuensis Tagawa as new hyperaccumulators of As and re-confirmed Pteris cretica as a hyperaccumulator. The average As concentration ranged from 1770 to 3650 mg kg(-1) DW in the fronds and 182 to 507 mg kg(-1) DW in the roots of P. cretica, P. biaurita, P. quadriaurita and P. ryukyuensis after having been grown in 100 mg As kg(-1) soil. There was a greater percentage of As(III) as compared to As (V) in the fronds of these plants. Based on our study, P. ryukyuensis is the most promising candidate to phytoremediate As contaminated soils compared to the other three species. The nutrient requirements or distributions within the Pteris species were altered distinctly when the plants were exposed to As.

Arsenic↗

Environmental costs of mercury pollution.

Mercury (Hg) has been used for millennia in many applications, primarily in artisanal mining and as an electrode in the chlor-alkali industry. It is anthropogenically emitted as a pollutant from coal fired power plants and naturally emitted, primarily from volcanoes. Its unique chemical characteristics enable global atmospheric transport and it is deposited after various processes, ultimately ending up in one of its final sinks, such as incorporated into deep sediment or bioaccumulated, primarily in the marine environment. All forms of Hg have been established as toxic, and there have been no noted biological benefits from the metal. Throughout time, there have been notable incidents of Hg intoxication documented, and the negative health effects have been documented to those chronically or acutely exposed. Today, exposure to Hg is largely diet or occupationally dependent, however, many are exposed to Hg from their amalgam fillings. This paper puts a tentative monetary value on Hg polluted food sources in the Arctic, where local, significant pollution sources are limited, and relates this to costs for strategies avoiding Hg pollution and to remediation costs of contaminated sites in Sweden and Japan. The case studies are compiled to help policy makers and the public to evaluate whether the benefits to the global environment from banning Hg and limiting its initial emission outweigh the benefits from its continued use or lack of control of Hg emissions. The cases we studied are relevant for point pollution sources globally and their remediation costs ranged between 2,500 and 1.1 million US dollars kg(-1) Hg isolated from the biosphere. Therefore, regulations discontinuing mercury uses combined with extensive flue gas cleaning for all power plants and waste incinerators is cost effective.

Arctic Regions↗

A novel process utilizing subcritical water and nitrilotriacetic acid to extract hazardous elements from MSW incinerator fly ash.

An effective process for hazardous element extraction from municipal solid waste incinerator fly ash was developed. The key trait of the process was to extract most of the hazardous elements out of the ash but leave Ca and Si inside the residue. In the extraction process, the ash was firstly pre-washed with water, then subjected to subcritical water (SC water) treatment and nitrilotriacetic acid (NTA) extraction. SEM images indicated that SC water is strong enough to destroy the ash particles, thus greatly improving hazardous elements extraction efficiency in the subsequent NTA extraction process. The extraction percentages for Cr, As, Se, Cd and Pb under SC water+NTA treatment were around 2-6 times higher than those treated by NTA at room conditions. The preferable SC treatment temperature was 573 K and the treatment time was 3 h. The optimum NTA concentration, vibration time and liquid/solid ratio were 0.8 M, 5 h and 10:1 (ml/g), respectively. Furthermore, it was found that introduction of a suitable amount of sulfuric acid into the extraction solution could extract more than 90% of most of the hazardous elements out of the ash.

Carbon↗

Mobilisation and attenuation of boron during coal mine rehabilitation, Wangaloa, New Zealand.

Environmental mobility and fate of boron has been traced from source to discharge waters through the rehabilitated Wangaloa coal mine in southern New Zealand. The boron is derived initially from coal, which has up to 450 mg/kg B. The coal also contains pyrite (2-5 wt.% S), which oxidizes to yield a low-pH environment (typical pH 2-5). Weathering of coal-bearing waste rock liberates B into rainwater that infiltrates into waste rock or evaporates to leave a gypsum crust enriched in B, possibly as boric acid or colemanite as inferred from geochemical modelling. Surface waters dissolve this evaporative material periodically, yielding total B concentrations up to 6 mg/L, at pH<4.5. Some of the available B is taken up by plants that have been established on the waste rock, resulting in foliage B concentrations of up to 230 mg/kg (dry weight). Partial attenuation of dissolved B by adsorption to iron oxyhydroxide occurs as groundwater passes through waste rock, but this is inhibited by adsorption competition with dissolved sulphate (up to 600 mg/L). Groundwater flows from the mine through a pit lake and wetland, with total dissolved B near 1 mg/kg after dilution and limited adsorption attenuation has occurred. Despite the widespread B mobility throughout the rehabilitated mine, there is little evidence of B toxicity in plants. The B concentrations in discharging waters are in the environmentally safe range for most aquatic organisms, being neither deficient in B as a micronutrient, nor boron-toxic.

Boron↗

Exposure to aerosolized bacteria and fungi among collectors of commercial, mixed residential, recyclable and compostable waste.

Biological hazards associated with the collection of solid and compostable waste have not been well characterized in North America. This is an issue because workers who handle such materials may be exposed to bioaerosols (airborne bacteria and fungi) and dusts resulting in infections or allergic diseases. We conducted a personal sampling campaign for culturable bacteria and fungi in the breathing zones of waste collectors in a variety of typical work settings (scenarios) in the province of Quebec, Canada. Total culturable bacterial and fungal counts were analyzed and compared to ambient environmental levels (background) to determine the degree of incremental exposure among workers. In several scenarios, worker exposure counts were significantly (p < or = 0.05) higher than ambient levels measured upwind, with the highest personal exposures to bacteria observed for urban compostable waste collectors (median = 50,300 Colony Forming Units/m(3) of air (CFU/m(3))). On the other hand, fungal counts collected on an every-other-week cycle were highest among a group of rural compostable waste collectors (median = 101,700 CFU/m(3)). Similar exposures to culturable bacteria and fungi have been reported in European workers who showed such adverse health effects as nausea, diarrhea, upper respiratory tract irritation, and allergy. Therefore, it may be necessary to modify certain work practices in order to minimize exposure. Recommendations include automation of waste and compost collection, use of personal protective equipment including goggles, gloves, and disposable masks, and meticulous personal hygiene.

Aerosols↗

Influences of carbonate and chloride ions on persulfate oxidation of trichloroethylene at 20 degrees C.

Application of in situ chemical oxidation (ISCO) involves application of oxidants to contaminants such as trichloroethylene (TCE) in soil or groundwater in place. Successful application of ISCO at a hazardous waste site requires understanding the scavenging reactions that could take place at the site to better optimize the oxidation of target contaminants and identification of site conditions where ISCO using persulfate may not be applicable. Additionally, estimation of the oxidant dose at a site would need identification of groundwater constituents such as alkalinity and chlorides that may scavenge radicals and therefore use up the oxidant that is targeted for the contaminant(s). The objective of this study was to investigate the influence of various levels of chloride and carbonates on persulfate oxidation of TCE at 20 degrees C under controlled conditions in a laboratory. Based on the results of the laboratory experiments, both chloride and alkalinity were shown to have scavenging effects on the rate of oxidation of TCE. It was found that at a neutral pH, persulfate oxidation of TCE was not affected by the presence of bicarbonate/carbonate concentrations within the range of 0-9.20 mM. However, the TCE degradation rate was seen to reduce with an increase in the level of carbonate species and at elevated pHs. TCE degradation in the presence of chlorides revealed no effect on the degradation rate especially at chloride levels below 0.2 M. However, at chloride levels greater than 0.2 M, TCE degradation rate was seen to reduce with an increase in the chloride ion concentration. Prior to application of persulfate as an oxidant, a site should be screened for the presence of scavengers to evaluate the potential of meeting target cleanup goals within a desirable timeframe at the site.

Carbonates↗

Bio-effect monitoring using a [(15)N]methacetin test as diagnostic tool to monitor remediation effects in an industrially polluted region.

The classical way to demonstrate the efficiency of remediation is measuring the reduction of toxic compounds in the environment. Nevertheless, more important is the risk reduction in human health. To determine changing health effects, exposure and bio-effects have to be monitored at time of and during remediation. Kindergarten children from a heavily polluted industrial (n=23) and a control area (n=12) were investigated. The region-specific outdoor and indoor exposure [27 volatile organic compounds (VOC), emphasis on tri- and tetrachloroethylene (TRI, TETRA)], the internal load [(trichloroacetic acid-TCA-as urine metabolites of TRI and TETRA and S-phenyl- and S-benzylmercapturic acid (SPMA and SBMA) as metabolites of benzene and toluene], and biological effect assessment ([(15)N]methacetin test-a non-invasive stable isotope test to determine the unspecific liver detoxification capacity of an individual) were measured twice a year during 2 years of remediation (1997/1998). It could be shown that in- and outdoor levels of TRI and TETRA decreased by 47% in the heavily polluted village, Greppin, while the levels remained much the same in the control village, Roitzsch. This trend was reflected in the decreasing elimination of TCA in the urine (41%) by the Greppin children, with no differences in the TCA elimination in Roitzsch probands. As the remediation efforts decreased the burden of exposure, the children's liver detoxification capacity improved as well. Combining different methods, such as exposure-effect (external and internal loads) and bio-effect monitoring, proved to be useful to assess remediation successes including the improvement in human health.

Acetamides↗

Assessment of soil remediation workers' exposure to polycyclic aromatic hydrocarbons (PAH): biomonitoring of naphthols, phenanthrols, and 1-hydroxypyrene in urine.

Urinalysis of multiple polycyclic aromatic hydrocarbons (PAH) biomarkers has been applied to assess the exposure of soil remediation workers on a former creosote wood impregnation site polluted with creosote oil. The uptake of PAHs was measured in preshift, end-of-shift, evening, and next preshift specimens (n=33) of nine volunteers with diverse tasks, using sensitive HPLC-FD methods. The ranges of biomarker concentrations in urine (nmol/l) were: 1-naphthol (14-159), 2-naphthol (9-166), 1- plus 2-naphthol (35-269), 1-hydroxyphenanthrene (OHPhe) (6-56), 2- plus 3-OHPhe (6-70), 4-OHPhe (1-6), 9-OHPhe (1-7), the sum of phenanthrols (15-135), and 1-hydroxypyrene, OHP (2.2-67). Eight of nine workers had OHP levels higher than the Finnish biological limit value for non-occupationally exposed persons (3nmol/l). A linear correlation was observed between 1- and 2-naphthol (r=0.90). The biomarker OHP correlated well in urine both with the major (1-OHPhe, r=0.96; 2- plus 3-OHPhe, r=0.84) and the minor phenanthrene metabolites (4-OHPhe, r=0.77; 9-OHPhe, r=0.68), and with the sum of all phenanthrols (r=0.94), but not so well with the sum of naphthols (r=0.66, p<0.001). The smokers had 2.9-, 2.2-, and 4.8-fold higher average concentrations of naphthols, phenanthrols, and OHP, respectively, than the non-smokers. The PAH biomarker data (concentrations and diurnal excretion profiles) showed significant work-related exposure in both non-smoking and smoking subjects. The average exposure levels were clearly higher than those we have measured for instance in asphalt paving workers. The workers' exposure should be assessed by biological monitoring, because at this type of outdoor work the dermal and pulmonary uptake of PAHs are both likely. Adequate measures for preventing, particularly, dermal absorption are of crucial importance for reducing the workers' risk of exposure to carcinogens on soil remediation sites.

Biomarkers↗

Acoustically assisted removal of nitrogen oxide from high temperature flue gas.

The present study focuses on a possibility for improving NO removal efficiency from flue gas by application of powerful sound waves. The sound waves (frequency 6.9-17.2kHz, intensity 144-160dB) are propagated from Hartmann sound generators to a preheated graphite disk inside a vertical reaction tube (height 1.8m, I.D. 105mm). An Ar-NO synthetic mixture (NO 911-934ppm) is blown onto the disk surface to perform reactions in the system C-NO. It is found that the NO reduction rate can be significantly enhanced by the sound waves but the enhancement effect is dependent on the sound frequency, intensity and temperature of disk surface. The better effects are obtained at a temperature of 973K and sound frequencies between 9.6 and 12.4kHz. Under these conditions, the sound application results in 3-5-fold enhancement of NO reduction rate. The obtained effects are explained in terms of gas-phase mass transfer controlling mechanism and of near surface turbulent diffusivity.

Acoustics↗

Effect of ultrasonic irradiation on nucleation phenomena in a Na2HPO4.12H2O melt being used as a heat storage material.

The effect of ultrasound on nucleation phenomena in the heat storage material Na2HPO4.12H2O was investigated by determining the primary nucleation probability and induction time, and by looking at heat generation phenomena in the initial stage of nucleation. The experimental results show that the primary nucleation probability dramatically increased, and the induction time decreased under the ultrasound irradiation, and in addition, the rate of temperature rise was dependent upon the ultrasonic output. Based on these results and the theoretical relationship between the number of primary nuclei and the heat generation rate, it is proposed that the number of primary nuclei depends upon the ultrasonic output.

Crystallization↗