Determination of toxic metals in discarded Liquid Crystal Displays (LCDs)

This study focused on the determination of the toxic metal content of Liquid Crystal Displays (LCDs) present in various Waste Electrical and Electronic Equipment (WEEE). The main objective was the identification and quantification of toxic metals detected in LCD panels. An experimental procedure which involved dismantling, shredding, pulverization, digestion and chemical analysis was followed for the sorting, separation and analysis of LCD monitors from various electronic devices that are currently on the market. Nine selected devices were examined, originated from four different types of e-waste (WEEE); TVs, computers, mobile phones and tablets. Eleven metals were measured in all examined samples. In addition, concentration values of chromium (Cr), cadmium (Cd), lead (Pb) and mercury (Hg) were compared with the respective limits set by the RoHS 2002/95/EC Directive that was recently renewed by the 2012/19/EU recast. The comparison revealed that the examined toxic metals on LCD panels did not exceed the limits set by the European Union (EU). Furthermore, when results were compared to the TTLC regulatory limits it was revealed that in three samples As concentrations were higher than the limit. Finally, when the TCLP test was implemented the aforementioned samples did not exhibit proportionally elevated values in their leachates.     

Spatial variations in selected metal contents and particle size distribution in an urban and rural atmosphere of Islamabad, Pakistan

Spatial variations in total suspended particulate matter (TSP) were investigated for distribution of metals and particle size fractions in the urban and rural atmosphere of Islamabad, Pakistan. The metals Na, K, Fe, Mn, Pb, Cd, Cr, Zn, Ni and Co, and the particle fractions <2.5, 2.5-10, 10-100 and >100 microm were included in the study. TSP samples were trapped on glass fibre filters using high volume samplers and quantification of metals was done using Atomic Absorption Spectrometry employing HNO(3) based wet digestion. At the urban site, Na was dominant at 2.384 microg/m(3) followed by K, Fe and Zn with 0.778, 0.667 and 0.567 microg/m(3) as mean concentrations, respectively. The metal levels for the rural site ranged from 0.002 microg/m(3) for Cd to 1.077 microg/m(3) for Na. However, compared with the urban site, mean Pb concentration showed an almost two-fold enhancement, i.e., 0.163 Vs. 0.327 microg/m(3). Metals and particle size source identification was done using Principal Component Analysis and Cluster Analysis. Five sources were traced out for the urban site: industrial, soil, automobile emissions, metallurgical industries and excavation activities. For the rural site, four sources were recorded: agricultural, automotive emissions, excavation activities and metallurgical units. Collectively, for both the sites, PM(10-100) emerged as a major contributor to TSP, followed by PM(2.5-10), PM(<2.5) and PM(>100) in that order. The metals showed in general positive relationship with fine particulate fractions (PM(2.5-10), PM(<2.5)), and negative correlation with coarse fractions (PM(10-100), PM(>100)). Comparison with the corresponding data from various Asian sites revealed that the levels of Na, K, Fe, Mn, Co and Ni for the present study were lower than those reported for grossly polluted cities of the world.     

Preliminary investigation of air bubbling and dietary sulfur reduction to mitigate hydrogen sulfide and odor from swine waste

When livestock manure slurry is agitated, the sudden release of hydrogen sulfide (H(2)S) can raise concentrations to dangerous levels. Low-level air bubbling and dietary S reduction were evaluated as methods for reducing peak H(2)S emissions from swine (Sus scrofa) manure slurry samples. In a first experiment, 15-L slurry samples were stored in bench-scale digesters and continuously bubbled with air at 0 (control), 5, or 10 mL min(-1) for 28 d. The 5-L headspace of each digester was also continuously ventilated at 40 mL min(-1) and the mean H(2)S concentration in the outlet air was <10 microL L(-1). On Day 28, the slurry was agitated suddenly. The peak H(2)S concentration exceeded instrument range (>120 microL L(-1)) from the control treatment, and was 47 and 3.4 microL L(-1) for the 5 and 10 mL min(-1) treatments, respectively. In a second experiment, individually penned barrows were fed rations with dietary S concentrations of 0.34, 0.24, and 0.15% (w/w). Slurry derived from each diet was bubbled with air in bench-scale digesters, as before, at 10 mL min(-1) for 12 d and the mean H(2)S concentration in the digester outlet air was 11 microL L(-1). On Day 12, the slurry was agitated but the H(2)S emissions did not change significantly. Both low-level bubbling of air through slurry and dietary S reduction appear to be viable methods for reducing peak H(2)S emissions from swine manure slurry at a bench scale, but these approaches must be validated at larger scales.     

Influence of nutrient levels on uptake and effects of mercury, cadmium, and lead in water spinach

In Southeast Asia the aquatic macrophyte water spinach (Ipomoea aquatica Forsk.) is a popular vegetable that is cultivated in freshwater courses. These often serve as recipients for domestic and other sorts of wastewater that often contain a variety of pollutants, such as heavy metals. In addition, fertilizers are frequently used where water spinach is cultivated commercially for the food market. To estimate the importance of ambient nutrient concentrations for accumulation of mercury (Hg), cadmium (Cd), and lead (Pb) in water spinach, plants were exposed to nutrient solutions of different strength and with varying metal concentrations. Metal-induced toxic effects, which might possibly affect the yield of the plants, were also studied. The lower the nutrient strength in the medium was, the higher the metal concentrations that accumulated in the different plant parts and the lower the metal concentration in the medium at which metal-induced toxic effects occurred. Accordingly, internal metal concentrations in the plants were correlated to toxic effects. Plants exposed to metals retained a major proportion of the metals in the roots, which had a higher tolerance than shoots for high internal metal concentrations.     

Selenium Bioaccumulation in Stocked Fish as an Indicator of Fishery Potential in Pit Lakes on Reclaimed Coal Mines in Alberta, Canada

Pit lakes are a common reclamation strategy for open pit mines; however, there is a concern about their water quality and suitability as fish habitat because they are often contaminated by metals or metalloids. This study assessed the exposure of fish and invertebrates to selenium (Se) and other metals and metalloids in pit lakes formed by open pit coal mining in Tertiary (thermal coal) and in Cretaceous (metallurgical coal) bedrock. Juvenile hatchery rainbow trout, Oncorhynchus mykiss, and brook trout, Salvelinus fontinalis, were stocked into two thermal coal pit lakes (water Se < 2 μg/L, low water Se) and two metallurgical coal pit lakes (water Se > 15 μg/L, high water Se). Se accumulation in stocked fish and concentrations in invertebrates were characterized over a period of 2 years. In the metallurgical pits, invertebrates had higher Se concentrations and fish accumulated Se to higher levels (exceeding USEPA tissue Se guidelines) than biota in the thermal pits. Rainbow and brook trout accumulated similar concentrations of Se in their muscle and exhibited a similar relationship between whole-body and muscle Se concentrations. These results may be used by resource managers to assess compliance with whole-body tissue Se guidelines and to determine if pit lakes in coal mining areas pose a significant Se risk to wildlife or human health. The high Se exposure in metallurgical coal pits indicates that under the current mining and reclamation strategy, these lakes are not suitable for management as recreational “put and take” fisheries.     

生活垃圾焚烧中重金属行为的研究进展

垃圾中的金属以氧化物、氮化物、碳化物及其它形态转移到焚烧产物如烟气、飞灰和底灰中，需严格控制焚烧过程中重金属的排放，故清楚了解金属在焚烧中的行为是很必要的。经研究发现，飞灰中重金属含量远远大于底灰中的含量，因此以垃圾焚烧飞灰中重金属的稳定化处理为目标，分析了目前国内外处理垃圾焚烧飞灰的方法和重金属在各种影响因素下的行为，并进行了比较，为飞灰的无害化和资源化处理提供参考。     

Effects of impurities on the removal of heavy metals by natural limestones in aqueous systems

Effects of impurities on the removal of heavy metals by natural limestones in aqueous solutions were studied by evaluating various factors including limestone concentration, pH, contact time and temperature. Solutions of Pb(II), Cd(II), Cu(II) and Zn(II), prepared from chloride reagents at a concentration of 10 mg/L, were studied in a batch method. Four natural limestone samples, collected from the Campanian-Maastrichtian limestone beds in Tunisia, were used as adsorbents. Sorption experiments indicated that high removal efficiencies could be achieved. Limestone samples containing impurities, such as silica, iron/aluminum oxides and different kinds of clay minerals, demonstrated enhanced sorption capacity, nearing 100% removal in some cases. Kinetic experiments showed that the sorption of metal ions occurred rapidly at a low coverage stage, and that solutions were nearly at equilibrium after 60 min. Data trends generally fit pseudo-second order kinetic, and intra-particle diffusion, models. The following conditions were found to promote optimum, or near-optimum, sorption of heavy metals: 1) contact time of more than 60 min, 2) pH = 5, 3) >3 g/L limestone concentration and 4) T = 35 °C. The results of this study suggest that the limestones from northern Tunisia, that contain higher amounts of silica and iron/aluminum oxides, are promising adsorbents for the effective removal of toxic heavy metals from wastewaters.     

浙江省废旧金属再生利用的经验、问题及对策

文章分析了浙江省在废旧有色金属资源再生利用方面的几个典型模式的经验、存在问题及发展对策。     

Copper lability in soils subjected to intermittent submergence

Reducing conditions in soils can have significant influences on the availability of nutrient and toxic metals, through their remobilization, their release through reductive dissolution of oxide phases, and from the formation of precipitates. In the literature, contrasting results are reported on the effects of temporary waterlogging conditions on the availability of metals. In the present study, changes in the "labile" or "potentially available" pool of copper (Cu) in soils as a consequence of up to three intermittent soil submergence cycles was investigated using isotopic dilution. The soils (an Oxisol and an Inceprisol) selected were amended in the field with both biosolids-Cu and salt-Cu. Intermittent soil submergence was found to have a significant effect on the lability of Cu in soils, with E(total) values generally increasing in all the treatments with the different submergence cycles, the highest lability of Cu observed in the Cu-salt treatment. The presence of nonexchangeable colloidal forms of Cu, influenced by treatments and submergence cycles, was also reported.     

Elemental contaminants in groundwater: A study of trace metals from residential area in the vicinity of an industrial area in Lagos, Nigeria

Groundwater (well water) from a residential area within the vicinity of an industrial estate in Lagos, Nigeria were sampled and analysed by Flame Atomic Absorption Spectroscopy for their heavy metals content. This was with a view of assessing the quality of the water, which was being used for domestic activities, especially, drinking usually without treatment. Total trace metal determination by mineral acid digestion of water samples was applied. This method proved to be better than an extractive concentration technique in the quality assurance protocols with the recovery range being 90.7 ± 0.006–97.6 ± 0.003%. Mean concentration of trace metals in water samples ranged from Fe: 0.05–0.47 mg l⁻¹; Al: 0.1–1.54 mg l⁻¹; Cu: 0.14–1.39 mg l⁻¹; Zn: 0.04–0.43 mg l⁻¹; Cd: trace–0.02 mg l⁻¹; Pb: trace–0.03 mg l⁻¹, Mn: 0.01–0.18 mg l⁻¹ and Ni: 0.02–0.11 mg l⁻¹. Physical parameters of water samples examined were within the drinking water safety limits except for conductivity. Results generally indicate the presence of heavy metal constituents in groundwater samples. Detection of metals such as cadmium and lead which have serious health implications above WHO and USEPA limits in drinking water gives cause for concern.     

Accretion of heavy metals in the catfish <Emphasis Type="Italic">Bagrus bayad</Emphasis> from Taylor Creek,southern Nigeria

Heavy metals in the aquatic environment have, to date, come essentially from naturally occurring geochemical resources. However, this has been enhanced by anthropogenic activities such as crude oil exploration and exploitation activities, resulting in pollution in the Taylor Creek aquatic ecosystem. The catfish species Bagrus bayad and other environmental segments were collected from five selected sites along Taylor Creek, southern Nigeria, and total metal concentration determined. The concentration levels of the metals in B. bayad were higher than the values reported in the literature for fresh fish and may lead to a higher risk of harmful effects. The bivariate regression models relating metals in B. bayad and metals in the surface waters were significant (R ² ≥ 0.9002). The log (bio-concentration factor; BCF) values of Cr and Zn in B. bayad were the highest, whereas the lowest was found for Ni. The ecological distribution of the log (BCF) values was, for all the heavy metals, moderately stable over the creek. All log-transformed bio-magnification factors (BMF) in the creek were positive, which indicates that the metal concentration was greater in B. bayad than in suspended particulate matter (SPM). The absolute log (BMF) values of heavy metals can, therefore, be ranked in order of decreasing magnitude: Cr (3.26) > Zn (2.99) > Cd (2.93) > Fe (2.76) > Pb (2.66) > Mn (2.36) > Ni (2.24). This sequence indicates that toxic metals such as Cd, Cr and Pb are undergoing significant bio-reduction from SPM to B. bayad. The degree of correlation between the metals was different in B. bayad, which suggests that the sources of the metals polluting Taylor Creek were diverse.     

A waste management planning based on substance flow analysis

The paper describes the results of a municipal solid waste management planning based on an extensive utilization of material and substance flow analysis, combined with the results of specific life cycle assessment studies. The mass flow rates of wastes and their main chemical elements were quantified with a view to providing scientific support to the decision-making process and to ensure that the technical inputs to this process are transparent and rigorous. The role of each waste management option (recycling chains, biological and thermal treatments), as well as that of different levels of household source separation and collection (SSC), was quantitatively determined. The plant requirements were consequently evaluated, by assessing the benefits afforded by the application of high quality SSC, biological treatment of the wet organic fraction, and thermal treatment of unsorted residual waste. Landfill volumes and greenhouse gas emissions are minimized, toxic organic materials are mineralized, heavy metals are concentrated in a small fraction of the total former solid waste volume, and the accumulation of atmophilic metals in the air pollution control residues allows new recycling schemes to be designed for metals. The results also highlight that the sustainability of very high levels of SSC is reduced by the large quantities of sorting and recycling residues, amounts of toxic substances in the recycled products, as well as logistic and economic difficulties of obtaining very high interception levels. The combination of material and substance flow analysis with an environmental assessment method such as life cycle assessment appears an attractive tool-box for comparing alternative waste management technologies and scenarios, and then to support waste management decisions on both strategic and operating levels.     

Comparison of trace metal contents of sediments and mussels collected within and outside Tolo Harbour,Hong Kong

Sediments collected from Tap Mun (within Tolo Harbour) and Yim Tin Tsai (outside Tolo Harbour) were extracted sequentially and the copper, cadmium, and chromium contents were determined. Total contents of copper, cadmium, chromium, and arsenic were also detected by acid digestion. The level of heavy metal extracted was higher in sequential extraction (which extracted all forms of metal ions) than total acid digestion. Among the four heavy metals studied, only copper showed a significantly higher (P<0.001) level in samples collected from Yim Tin Tsai (16.10 mg/kg) than that from Tap Mun (3.19 mg/kg). Such a difference in copper level is mainly attributed to the significantly higher (P<0.05) levels of copper in the organic, carbonate, and sulfide forms, whereas there was no significant difference (P>0.05) in the exchangeable and sorbed forms. Green-lipped mussel (Perna viridis) samples collected from the two sites were dissected into seven parts (gill, byssus, siphon, shell, digestive gland, soft tissue, and adductor muscle) and the concentrations of copper, cadmium, chromium, and arsenic were measured. The highest concentration of copper was obtained in the byssus. A higher concentration of copper was also noted in the mussels collected from Yim Tin Tsai than those collected from Tap Mun. No specific trend was revealed for the other metals tested. Chromium and arsenic concentrations were found to be independent of the body size of the mussels. Copper had a lower concentration in larger mussels and cadmium level was found to decrease with size. In addition, the mussels collected from Tap Mun were much larger than those collected from Yim Tin Tsai.     

POLLUTANT REMOVAL FROM COAL-ASH BASIN EFFLUENT1

ABSTRACT: The drainage system for an ash basin serving a coal-fired power plant at the Savannah River Project, Aiken, South Carolina, has been studied for 15 months to determine abiotic and biotic characteristics and mechanisms of pollutant removal. Measurements made included temperature, dissolved oxygen, pH, turbidity, alkalinity, conductance, flow rate, sulfate, nitrate, and phosphate. In addition, neutron activation analysis was employed to determine concentrations of 40 chemical elements in water, benthos, bacterial, plant, invertebrate, and vertebrate samples collected at six sampling stations. Five-day toxicity tests were performed using organisms from within and from outside the system. Conductance, pH, alkalinity and sulfate concentration varied little throughout the system. Temperature, dissolved oxygen, turbidity, nitrate, phosphate, and flow rate decreased at stations farther removed from the ash basin. Concentrations of most chemical elements measured were greatest in benthos (75 percent of total) and least in water (less than one percent of total), indicating that a major removal mechanism was sedimentation of suspended particulate matter. Eight elements (Br, Ca, C1, Cd, Na, Sb, Se, and Zn) were more highly concentrated in one or more biotic forms than in benthos. Among heavy metals only Cr was concentrated to a greater extent by plants than by animals. Midges were the greatest concentrators of Fe, Cu, Cr, Hg, Co, Sb, and As among all organisms. Plants concentrated only 15 percent of the total heavy metal concentration found in the benthos. Light, metals were more highly concentrated in animals than in plants, although all plants were found to possess 19 percent of the concentration present in the benthos and water. As and Sb were in low concentration within the system; however, on a percentage basis, these potentially toxic elements were relatively highly concentrated by a number of organisms. Active metals (Ca, Na, and K) and halogens (CI, Br, and I) were highly concentrated by most organisms. Active metals were more concentrated in crayfish and mosquito fish, Gambusia affinis, than in benthos, whereas most organisms had higher concentrations of halogens than were found in benthic sediments. Primary producers within the system were least efficient in concentration of all elements except Mn. Consumers (invertebrates and vertebrates) were found to possess highest concentrations of all other elements. Organisms found within the drainage system were observed to be able to survive a five-day toxicity test at any point within the system, whereas organisms not existing within the system were observed to vary in their resistance to the drainage system environment. The findings of this study demonstrate the necessity for the operation of entire food chains in pollutant removal and indicate potential means for increasing cycling efficiency by selective addition of resistant consumers to such a system.     

Toxicity of ozonated animal manure to the house fly, Musca domestica

Swine manure slurries were ozonated at a dosage of 1 g/L and tested for their toxicity to the house fly (Musca domestica). The observed toxicity of ozonated swine manure was consistent and independent of origin of the swine manure. A dose (dilution) response curve was performed. A 50% dilution in the ozonated swine manure slurry resulted in 90% reduction in toxicity. Neither the synthetic nor ozonated synthetic swine manure, both of which contained higher concentrations of formaldehyde and three other unidentified carbonyl compounds than the ozonated swine manure, were toxic to the flies. Ozonated swine manure slurry was centrifuged and passed through a 0.45-microm filter. The liquid phase was as toxic as the unfiltered slurry; as such, the toxicant appears to be present in liquid phase. Neither ammonia, hydrogen sulfide, formaldehyde, nor other simple aldehydes appeared to be the toxic agent. The toxic agent appears to be a polar chemical compound and is concentrated in the urine. Several possible compounds have been identified. The toxicity of untreated and ozonated manure slurries from different livestock was compared. Six animal manure slurries (beef and dairy cattle, horse, poultry, sheep, and swine) were ozonated (dosage of 1 g/L) and tested for toxicity to the house fly. Ozonated dairy cattle manure slurry showed 78% mortality after 72 h, whereas ozonated swine manure slurry achieved a 100% mortality rate in 48 h. Neither the unozonated dairy nor swine manure slurries, nor any of the other raw or ozonated manure slurries, were toxic to the flies.     

Characterization of pollutants in Florida street sweepings for management and reuse

Disposal and beneficial-use options for street sweeping residuals collected as part of routine roadway maintenance activities in Florida, USA, were assessed by characterizing approximately 200 samples collected from 20 municipalities. Total concentrations (mg/kg or μg/kg) and leachable concentrations (mg/L or μg/L) of 11 metals and a number of organic pollutant groups (volatile organics, semi-volatile organics, pesticides, herbicides, carbamates) in the samples were measured. The synthetic precipitation leaching procedure (SPLP) was performed to evaluate the leachability of the pollutants. From the total metal analysis, several metals (e.g., arsenic, barium, chromium, copper, nickel, lead, and zinc) were commonly found above their detection limits. Zinc was found to have the highest mean concentration of all metals measured (46.7 mg/kg), followed by copper (10.7 mg/kg) and barium (10.5 mg/kg). The metal with the smallest mean concentration was arsenic (0.48 mg/kg). A small fraction of the total arsenic, barium, lead, and zinc leached in some samples using the SPLP; leached concentrations were relatively low. A few organic compounds (e.g., 4,4′-DDT, endrin, and endosulfan II) were detected in a limited number of samples. When the total and leaching results were compared to risk-based Florida soil cleanup target levels and groundwater cleanup target levels, the street sweepings were not found to pose a significant human-health risk via direct exposure or groundwater contamination.     

Phenol degradation using combined effects of hydrodynamic cavitation and oxidant: Doehlert matrix

Hydrodynamic cavitation (HC)-based treatments have been proposed for the degradation of phenol as a toxic pollutant. The present work aimed to optimize the degradation of phenol using HC by means of Doehlert experimental design, which has not been previously addressed. Initially, operational parameters of hydraulic characteristics of the pump, inlet pressure, solution pH, and initial concentration were optimized; later, the effects of pH solution and H₂O₂ loading or initial pollutant concentration on phenol degradation were explored using the Doehlert experimental design. It was observed that phenol degradation is strongly dependent on the pH of the solution. Also, the acidic condition favors the formation of hydroxyl radicals and thus, the degradation of phenol. Based on the Doehlert matrix, the 94.1% phenol degradation and 68.60% total organic carbon (TOC) were obtained in 180 min at 304.5 mg/L of hydrogen peroxide at an initial concentration of 20 mg/L, 2.0 pH, and 90 psi inlet pressure, providing a cavitational yield of 6.33 × 10⁻⁶ mg/J and minimum treatment cost of US$/L 0.13. Overall, it has been observed that HC can be a promising route for the removal of pollutants (phenol) effectively using hydrogen peroxide as an additive.     

Impact of market reforms on future patterns of non-ferrous metal consumption of the former Soviet Union

The study examines the implications of market-oriented reforms on the prospects of non-ferrous metal use in the former USSR. Past metal consumption behaviour of the USSR is found to differ considerably from prevailing patterns of the advanced market economies. The study estimates a large 'intensity- of-use' gap across metals, which can be taken as a relatively easily mobilizable source for efficiency improvements via market reforms. Two scenarios for economic reforms are modelled, notably radical and gradual. Both are shown to cause a collapse of varying intensity in domestic metal demand lasting until the mid-1990s. For the subsequent period, a turnaround in consumption trends is projected, which is sharper under the radical reform scenario. The projected collapse of domestic demand argues for an increasing exportable surplus in the former Soviet Union for a range of non-ferrous metals, with potentially severe depressive effect on world prices.     

Freshwater Mussel Population Status and Habitat Quality in the Clinch River,Virginia and Tennessee,USA: A Featured Collection

The Clinch River of southwestern Virginia and northeastern Tennessee is arguably the most important river for freshwater mussel conservation in the United States. This featured collection presents investigations of mussel population status and habitat quality in the Clinch River. Analyses of historic water‐ and sediment‐quality data suggest that water column ammonia and water column and sediment metals, including Cu and Zn, may have contributed historically to declining densities and extirpations of mussels in the river's Virginia sections. These studies also reveal increasing temporal trends for dissolved solids concentrations throughout much of the river's extent. Current mussel abundance patterns do not correspond spatially with physical habitat quality, but they do correspond with specific conductance, dissolved major ions, and water column metals, suggesting these and/or associated constituents as factors contributing to mussel declines. Mussels are sensitive to metals. Native mussels and hatchery‐raised mussels held in cages in situ accumulated metals in their body tissues in river sections where mussels are declining. Organic compound and bed‐sediment contaminant analyses did not reveal spatial correspondences with mussel status metrics, although potentially toxic levels were found. Collectively, these studies identify major ions and metals as water‐ and sediment‐quality concerns for mussel conservation in the Clinch River.     

A quantitative estimate of potential aluminium recovery from incineration bottom ashes

The recovery of ferrous and non ferrous metals from the bottom ashes is a common practice in the most part of Europe, both for the environmental advantages of their recycle and to avoid problems of swelling and expansion that metals can cause when bottom ashes are reused in concrete production or in road construction. This paper focuses on metal recovery from bottom ashes produced in Municipal Solid Waste (MSW) incinerators, with a particular focus on aluminium. A forecasting model was developed in order to evaluate the quantity of aluminium scraps recoverable from the bottom ashes. The model was applied to the Italian situation but its validity can be extended to other countries. Focusing on Italy, by applying conventional technologies for the separation of non-ferrous metals, the amount of aluminium potentially recoverable from bottom ashes is estimated in the range from 16,500 to 21,000 tonnes at the year 2015, and from 19,000 to 28,500 tonnes at 2020.