澳大利亞西悉尼大學自然科學留學生dissertation-Mobility and Testing of heavy metals (Zn, Cu and Pb) 

 

 

ABSTRACT

In order to identify the solubility or pH value of the materials at Sunny Corner, the studied have been done in past. This study is done to experiment chemical assessment at abandoned metal mine at Sunny Corner. There has been done sampling for the contaminated metals there and then the experimental and analytical techniques were used for the analysis and identification. AAS (dilution), SEM and XRD methodologies were used and the solubility was tasted under water level of less than 0.3m from surface. It was found that the detection limit of carbonates in the water were of 0.5 mg per litre order. At the surface waters were soft, hard and oxidizing. The AAS- Perkin Elmer Analyst 100, technique in the present study resulted that at different pH level the concentration of Zn was highest than other Copper and Lead metals.為了確定在陽光明媚的角落的溶解度或材料的pH值，研究已經完成，在過去的。這項研究是在廢棄的金屬礦在陽光明媚的角落化學評價實驗。已完成的取樣重金屬污染之后，實驗和分析技術用于鑒定分析。原子吸收光譜法（稀釋），SEM和XRD方法和溶解度嘗小于0.3m地表水位下。結果發現，在水中碳酸鹽的檢測限為0.5毫克每升階。在地表水的軟，硬質氧化。火焰原子吸收光譜法-珀金埃爾默的分析師100，在本研究中，在不同的pH值水平的技術導致的Zn的濃度最高，比其他的銅和鉛的金屬。

 

Key words : Copper, Lead, Zinc, Mobility.

 

• INTRODUCTION

Sunny Corner is small village in New South Wales, Australia and also former mining area. According to 2006 census, the population of Sunny Corner was 626 only. Sunny Corner is considered as the silver town of 1880’s. There have been found many mines in the Sunny Corner Village and so the project is called ‘Sunny Corner Project’. Heavy materials such as Lead (Pb), Copper (Cu) and Zinc (Zn) have been in the mines at Sunny Corner. Lead (Pb), Zn and Cu are toxic heavy metal and this has occasioned many studies aimed at understanding its solubility behaviour in surface waters and how it may be mobilized in the supergene zone. The report has been furnished by Geological Surveyor, Mr. David (Sydney Mail, Oct 1890) that irregular cavities were found in Sunny Corner with regard to the underlying surface of the felstone dyke. Here, it has been found that at the 50 feet from the surface it made in to solid sulphite ores such as copper, iron, zinc, lead etc, containing a small percentage of gold and silver. At the mouth of Sunny Corner Number 3, there have been found 200 yards long mine for these heavy metal ores. 陽光的角落是小村莊在澳大利亞新南威爾士and also形成礦區。根據2006年的人口普查，人口of陽光角球was 626 only。陽光的角落is considered as the town of 1880年代的銀。There have been found in the many地雷陽光角村and so the project is called“陽光工程”的角落。重的材料，如鉛（Pb）銅（Cu）、鋅（Zn）have been in the地雷在陽光的角落。鉛（Pb），鋅和銅是有毒的重金屬和這有許多研究occasioned aimed at Understanding its溶解度行為在表面水域and how it may be mobilized in the淺成的區域。the report has been用by地質探勘者號，先生。大衛（悉尼郵件，OCT 1890年），不規則腔were found in陽光的角落with regard to the underlying表面of the魔石巖墻。在這里，it has been found that at the 50英尺from the表面它made in to固體亞硫酸鐵礦石如銅，鉛，鋅等，含有小百分比金和銀。at the mouth of陽光的角落number 3，there have been found 200碼長的煤礦for these金屬礦石。#p#分頁標題#e#

 

Volcanogenic Massive Sulphide style deposits ores were explored by Golden Cross Resources and during the extraction of gold and silver, 30% of the combined material of zinc, copper and lead were wasted. A total of 250,000 tonnes of sulphur have been originally mined at the sea floor. The materials at Sunny Corner are hosted in sequence of Siluro-Devonian rocks and later felsic porphyries. It has been reported by Adam Piestrzyński that the depth of the water is linked with the deposition of sulphide and so the resulting style of the mineralization. Massive Sulphide depositions were occurred at Sunny Corner, although these deposits have similar isotope distribution.  The studies show that increase in water depth enhances the deposition of the sulphides in sea –floor environment by preventing boiling of hydrothermal fluids. 

 

(Chapman et al. 1983) states in the research that metal contamination is heavily found at Sunny Corner. (Higgs 1991; Pettit 1979) suggests that the soil of the Sunny Corner is of low species richness and so the fertility is not oversexed there. These metals have oxidation sates -0, I, II, IV and all are found in nature. 

 

In this work, the assessment of the most contaminated materials have been studied and experimented. Assessment of trace materials (Cu, Pb and Zn) compositions in soil, sediments and water (<0.3 m below ground level), water analysis, solid phase analysis and Solubility have been experimented using AAS (dilution), SEM and XRD methodologies. The results of this study provide insights to the contaminated materials at Sunny Corner Mines with their various characteristics. 

 

 • MATERIALS AND METHODS

In order to gather the data for experiments, some of the important methods which were used are discussed below:

 

2.1 Soil Sampling Locations

 

Fig 1: Location of sampling sites along daylight Creek at Sunny Corner Mines

Three sites within the upper daylight creek region were selected for sampling and this site is located at the major contamination source of metal area. At these sites, soil, water and plants were sampled followed with the sampling procedure outlined by Crepin and Johnson (1993). 

 

 

2.2 XRD

X-Ray Diffraction method is non-destructive analytical technique which has been used for the analysis of the contamination materials. Here used model of XRD is the Bruker D8 Advance Powder Diffractometer. XRD samples were prepared by crushed a small amount in a mortar and pestle and mixed it with acetone then added it drop wise to that round plastic thing. XRD1, XRD4, XRD7 was done on the Phillips PW 1820 and the rest were done on the bucker. Run time for Phillips was about 45 minutes. The used software in this method is TOPAS.#p#分頁標題#e#

 

 

2.3 Water 

Water samples prepared by filtering off any solids using vacuum filter & filter paper, dilutions were only needed when the value was above the working range. Filtered them using Buchner vacuum filter to remove orange precipitate that had formed. Analysed them on the AAS, and if the reading was higher than the standard range we diluted them 1/10 and if it was still high we diluted it again 1/100. AAS model used was Perkin-elmer Analyst 100.

 

 

2.4 SEM

Small piece of SEM samples must be clean and dry before doing any SEM characterization. Then put in the sample holder and push inside the SEM for analyse. Joel jxa-840 scanning micro analyser was also used.

 

• RESULTS AND DISCUSSION

 

3.1 Heavy metals in Sunny Corner discharge waters

After sampling of the contaminated materials, waters were chilled in ice so that it can inhibit bacterial growth and adsorptive losses as mentioned in the research (Clesceri et al. 1989). The obtained samples were filtered using acid washed Whatman GF/C. These had the normal size as of 0.45 µm pore size. The detection limit was of the order of 0.5 Mg per litre. Based on the provided outlines by Chapman (1992) and Clesceri et al (1989), it was identified that at the surface waters were fresh, hard (>100 mg per litre CaCO3) and oxidizing. 

 

3.2 Location of Sample and Observation 

The samples were tested using XRD technique and it was found that different minerals were found on the different locations of the Sunny Corner Project. In XRD1 sample (outside of the cave) the mineral was identified as Copiapite, in XRD2 sample (inside of the cave) the mineral was Melanterite, in XRD3 sample (next to the cave) the mineral was Hohmannite, in XRD4 (above location of XRD3), and XRD 7 (XRD 4 location) the mineral were found Copiapite and Rozenite, in XRD6 the mineral was Quartz alpha or Arsenopyrite and in XRD5 (outside of the cave) there was no mineral obtained. 

 

3.3 pH value and heavy metal 

Using the AAS technique, with the prepared samples as DF samples, AS samples, and HA samples, the pH value for the identified minerals were detected to understand how the heavy contaminated metals have pH value. For pH value 2.69, concentration for Zn was highest (10), for copper the value is (6.65) and for Pb it was 0.647. This shows that the pH value changes with the type of materials. It was also observed that in few samples the concentration was only identified for Copper and Zinc but not for Lead.

 

• CONCLUSIONS

It has been shown from the researches and experiments that there are heavy minerals available at the Sunny Corner Location and sulphides are deposited even at the depth of 50 ft. Clesceri et al (1989), suggests that as the deposition of sulphides enhances with the depth of the water. The minerals were experimented using XRD, SEM technique at various locations, and it was found that at some locations there were minerals and at some it was not. Trace metals analysis shows that there is around 34% availability of minerals. The pH value test with AAS technique illustrates that the higher concentration of Zn was found in higher pH value sample. The overall results show that at Sunny Corner, Copper, Zinc and Lead is found in abundance. #p#分頁標題#e#

 

ACKNOWLEDGEMENTS

We thank Jason K.Reynolds and Richard Wuhrer for all useful information. Prof Williams and Prof Leverett for helping everyone. Tim for the helping XRD work, and Wayne for the AAS work.

 

REFERENCES 

Allen SE. 1989. Chemical Analysis of Ecological Materials. 2nd edn. Blackwell Scientific, Oxford, UK.

ANZECC (Australian and New Zealand Environment and Conservation Council). 1992. Australian Water Quality Guidelines for Fresh and Marine Waters. ANZECC Publication, Canberra, Australia.

Baker AJM, McGrath SP, Sidoli CMD and Reeves RD. 1994. The possibility of in situ trace metal decontamination of polluted soils using crops of metal-accumulating plants. Resour. Conserv. Recycl. 11, 41-49.

Baudo R, Giesey JP and Muntau H. 1990. Sediments: Chemistry and Toxicity of In-Place Pollutants. Lewis Publishers, Ann Arbor, Michingan, USA.

Bing M. 1996. Back to nature. Mining Voice July/August, 31-33. 

Black H. 1995. Absorbing possibilities: phytoremediation. Environ. Health Perspect. 103, 1106-1108.

 

Blaylock MJ, Salt DV, Dushenkov S, Zakharova O, Gussman C, Kapulnik Y, Ensley BD and Raskin I. 1997. Enhanced accumulation of Pb in Indian mustard by soil-applied chelating agents. Environ. Sci. Tech. 31, 860-865.

Bower CA, Reitemeier RF and Fireman M. 1952. Exchangeable cation analysis of saline and alkali soils. Soil Sci. 73(4), 251-261

 

Chapman D. 1992. Water Quality Assessments. A Guide to the Use of Biota, Sediments and Water in Environmental Monitoring.

 

Clesceri LS, Greenberg AE and Trussell RR. 1989. Standard Methods for the Examination of Water and Wastewater. 17th edition. APHA/AWWA/WPCF, Washington DC, USA

Shetty KG, Banks MK, Hetrick BA and Schwab AP. 1994a. Biological characterisation of a southeast Kansas mining site. Water, Air, Soil Pollut. 78, 169-177.

Captions of Tables

 

Table 1. XRD samples – Used for mineral identification at different locations at Sunny Corner Site.

 

Table 2. AAS testing results - AAS- Perkin Elmer AAnalyst 100, the pH value were identified for different samples and based on that the concentration of the materials as Cu, Zn, and Pb were identified. 

 

Table 1

Samples Mineral Name Where it was found

XRD 1 Copiapite Outside cave

XRD 2 Melanterite #p#分頁標題#e#Inside cave

XRD 3 Hohmannite Next to the cave

XRD 4 (Refer to XRD 7) Above the location of the XRD3 sample (wasn’t exposed to the sun)

XRD 5 N/A Outside cave (same location as XRD 1)

XRD 6 Quartz alpha or Arsenopyrite Top of the mountain

XRD 7 (Re-testing for XRD 4) Copiapite and Rozenite Refer to XRD 4 location

 

Table 2

AAS- Perkin Elmer AAnalyst 100

Sample pH Cu (mg/L) Zn (mg/L) Zn 1/10 (mg/L) Zn 1/100 (mg/L) Pb (mg/L) Fe (mg/L) Fe 1/10 (mg/L) Fe 1/100 (mg/L)

Standard Range 0-10 0-1.5 0-1.5 0-1.5 0-20 0-8 0-8 0-8

DF samples

A 2.69 6.65 10 8.5 2.1 0.647 110 12 -0.3

B 2.76#p#分頁標題#e# 6.733 10 8.5 2.1 0.805 110 13 0.18

C 2.79 6.798 10 8.5 2.1 0.947 110 14 0.51

D 2.81 6.369 10 8.4 1.9 0.938 97 11 0.45

E 2.77 6.111 10 8.3 1.7 1.03 87 9.1 -0.02

F 2.89 4.988 9.7 6.7 0.95 1.17 24 1.7 _

G 6.35 -0.055 #p#分頁標題#e#2.8 0.24 -0.02 0.46 -0.32 -0.71 _

H 3.7 1.223 8.8 2.6 0.27 0.736 0.06 -0.68 _

I (final) 3.2 1.22 8.8 2.7 0.27 0.67 -0.12 -0.68 _

AS samples

1 0.076 7.6

2 0.686 2.1

3 -0.037 60 #p#分頁標題#e#

4 -0.056 61

5 -0.069 3.3

6 0.148 0.73

7 -0.095 -0.36

8 0.05 -0.16 #p#分頁標題#e#

HA samples

1 -0.014 5.3

2 0.18 3

3 -0.831 9.2

4 0.073 4.8

5 0.808 -0.2

6 #p#分頁標題#e# 0.902 61

Tap Water 0.2 0.09

 

 

Captions of Figures

Figure 1. Mineral Melanterite found inside the cave using XRD technique 

Figure 2. Mineral Hohmannite were identified next to the cave using XRD technique

Figure 3. Mineral Hohmannite found next to the cave using XRD technique

Figure 4. Mineral Copiapite and Rozenite found next to the cave using XRD technique

Figure 5. Heavy metal found using SEM technique (bright area).

Figure 6. Heavy metal found using SEM technique (gray area).

Figure 7. Heavy metal found using SEM technique (gray brighter area).

Figure 8. Practical Result obtained with AAS technique for the sample obtained 

Figure 9. Beautiful scene from Sunny Corner

Figure 10. Beautiful scene from Sunny Corner

Figure 11. Beautiful scene from Sunny Corner