Dr J. Paul Chen Department of Chemical & Environmental Engineering

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Biosorption Process For Removal and Recovery of Heavy and Precious Metals from Aqueous Solutions: Past, Present and Future Dr J. Paul Chen Department of Chemical & Environmental Engineering National University of Singapore, Singapore Presented at International Symposium on Water Resources Wuhan, China November 9, 2003

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Biosorption Process For Removal and Recovery of Heavy and Precious Metals from Aqueous Solutions: Past, Present and Future. Dr J. Paul Chen Department of Chemical & Environmental Engineering National University of Singapore, Singapore - PowerPoint PPT Presentation

Transcript of Dr J. Paul Chen Department of Chemical & Environmental Engineering

  • Biosorption Process For Removal and Recovery of Heavy and Precious Metals from Aqueous Solutions: Past, Present and FutureDr J. Paul ChenDepartment of Chemical & Environmental Engineering National University of Singapore, SingaporePresented at International Symposium on Water ResourcesWuhan, ChinaNovember 9, 2003

  • Outline of PresentationMotivationHistorical backgroundCurrent developmentApplicationMechanismsFuture trendsSummary

  • Major Industries in SingaporeOriginally 7 islands of total area of 900haReclamation efforts: 2,650ha in 2001, to increase to 3,200ha in 200355 companies on site (e.g. DuPont, Chevron, Celanese, ExxonMobil, Eastman, Sumitomo)Target output from chemical industries: S$75 billion by 2010Jurong Island: Integrated Petrochemical Hub

    1S$=4.75 RMB

  • Chemical Industry

    Chemical Cluster Output : S$ 28.9 billion

    Chemical Output Share (2001)

    Petroleum62%

    Petrochemicals23%

    Specialty Chemicals15%

    Others1%

  • Major Industry Sectors (2001)

    Total Manufacturing Output : S$ 135 billion

    Engineering18.3%

    Chemicals20.8%

    General Industries1.4%

    Biomedical Sciences9.2%

    Electronics50.3%

  • Why do we care about metal contamination ?Human activities and natural processes inevitably would produce metal wastes.Typical industries are metal-plating and metal-finishing operations, e.g. semiconductormining and ore processing operations, metal processing, battery and accumulator manufacturing operations, thermal power generation (coal-fired plants in particular), nuclear power generation,Military practices, e.g. UNaturally occurring metal wastes include arsenic and arsenite.

  • Why do we care ... metal ? ContdEPAs have become more concerned the impacts.In the USA, important regulations are Cu-Pb and As rule (new ruling of 10-ppb AS in drinking water in 2001)Searching cost-effective technologies becomes crucial. Technologies:Precipitation, adsorption, ion exchange, electro-coagulation, electrochemical reduction, membrane filtration However, the costs and efficiencies still remain as a major concern.

  • Affinity of metal with organicsL-2-Aminopropanoic Acid (Alanine) with various metalMetal Ions1. Immobilization of organics; 2. use of organics in natural biosolids

  • Historical background: 1980-1995Biosorption by the materials derived directly and/or indirectly by various organisms has long recognizedHowever, the applications of biosorption started to appear in scientific literatures in early 1980s.Credit - One of earlier researchers, B. Volesky of McGill Univ., had contributed significantly by publishing a series of papers, mainly on screening of biosorbents and measurement of biosorptive capacities.

  • What is biosorption ?Biosorption is a property of certain types of inactive/active organisms to bind and concentrate heavy metals from even very dilute aqueous solutions. Biosorbents can be classified into:a. Inactive organisms (mainly) include algae, fungi and bacteria b. Their derivatives which are termed as biopolymers.Opposite to biosorption is metabolically driven active bioaccumulation by living substances.

  • What are typical biosorbents ?Some of the biomass types come as a waste by-product of large-scale industrial fermentations (the mold Rhizopus, the bacterium Bacillus subtilis and waste activated sludge). Other metal-binding biomass types, certain abundant seaweeds (particularly brown algae e.g. Sargassum, Ecklonia ), can be readily collected from the oceans. Biopolymers are normally extracted from inactive organisms and processed before use (e.g. Ca-Alginate)These biosorbents can accumulate in excess of 25% of their dry weight in deposited metals:Pb, Ag, Au, U, Cu.

  • Case presentsRaw seaweeds collected in SingaporeCa-alginate beadsCa-alginate based ion exchange resin (CABIER)

  • Examples: Marine Algal collected in SingaporePadina sp.Sargassum sp.

  • Why biosorption ? Cu sorption

  • Characterization of biosorbents by instrumental analysisFourier transform infrared spectroscopic (FTIR) and X-ray Photoelectron Spectroscopic (XPS) studies show that biosorbents have significant amount of COO, OH, C=O, and C-O.These organic functional groups would be responsible for metal uptake onto the biosorbents due to the high affinity for metal ions.SEM shows less pore development in bisorbents

  • Biosorption Equilibrium

  • Metal biosorptive properties: pH effectSOH + Mm+ = SO-Mm+ + H+ Sargassum Ca-alginate

    Chart1

    6.61666666672.0666666667

    8.63333333335.2

    9.066666666715.9733333333

    8.683333333315.8916666667

    5.216666666716.13

    1.516666666715.4733333333

    1.583333333315.4183333333

    1.1833333333

    1.3

    0.7833333333

    0.85

    0.6166666667

    Cr3+

    CrO4-

    Final pH

    q, mg/g

    Cr(VI)-isotherm(2)

    ObjectivesEquilibrium isotherm: biosorption of chromate

    Weight of Biomass0.15g

    Volume of solution0.05L

    pH of solution2

    CiCiCe (Set 1)Ce (Set 2)Ce (Avr)Ce (Avr)QQCe/qlnCelnQ

    mg/LmMmg/Lmg/Lmg/LmMmg Cr/ g biomassmM Cr/ g biomass

    21.50.418.488.488.480.164.340.081.95391705072.13771044981.4678743481

    41.60.8019.719.719.70.387.300.142.6986301372.98061863571.9878743482

    63.31.2232.432.132.250.6210.350.203.1159420293.47351804322.3369865197

    82.51.5947.846.947.350.9111.720.234.04125177813.85756681962.4610123296

    97.71.8860.259.359.751.1512.650.244.72332015814.09016919082.5376572152

    125.62.4278.88079.41.5315.400.305.15584415584.37449836832.7343675094

    2063.96151.2149.8150.52.8918.500.368.13513513515.01396308422.9177707321

    259.24.98194.4193.61943.7321.730.428.92638036815.26785815913.0788471803

    3065.882402322364.5423.330.4510.11428571435.4638318053.1498829534

    357.66.88286.4285.62865.5023.870.4611.98324022355.65599181083.1724827853

    4007.69323.2320.83226.1926.000.5012.38461538465.77455154553.258096538

    4488.62371.2372.83727.1525.330.4914.68421052635.91889385433.2321210516

    53010.19444447.5445.758.5728.080.5415.87240356086.09975825673.3351762806

    qmax=31.2531.2989045383

    b=0.01308472360.0130643855

    Cr(VI)-isotherm(2)

    4.34

    7.3

    10.35

    11.7166666667

    12.65

    15.4

    18.5

    21.7333333333

    23.3333333333

    23.8666666667

    26

    25.3333333333

    28.0833333333

    Ce (ppm)

    Q (mg Cr/ g biomass)

    Cr(VI)-isotherm (4)

    1.9539170507

    2.698630137

    3.115942029

    4.0412517781

    4.7233201581

    5.1558441558

    8.1351351351

    8.9263803681

    10.1142857143

    11.9832402235

    12.3846153846

    14.6842105263

    15.8724035608

    Ce, mg/L

    Ce/q

    Cr(VI)-isotherm (6)

    ObjectivesEquilibrium isotherm: biosorption of chromate

    Weight of Biomass0.15g

    Volume of solution0.05L

    pH of solution4

    CiCiCe (Set 1)Ce (Set 2)Ce (Avr)Ce (Avr)QQCe/qlnCelnQ

    mg/LmM/Lmg/Lmg/Lmg/LmM/Lmg Cr/ g biomassmM Cr/ g biomass

    21.80.415.215.115.150.292.220.046.83458646622.7180005320.796004566

    51.31.041.241.941.550.803.250.0612.78461538463.72689752131.1786549963

    82.91.665.567.366.41.285.500.1112.07272727274.19569705651.7047480922

    109.02.193.192.192.61.785.470.1116.93902439024.52828914171.6986690462

    167.03.21481441462.817.000.1320.85714285714.98360662171.9459101491

    215.04.1194195194.53.746.830.1328.46341463415.27043216311.9218125975

    336.06.5305306305.55.8810.170.2030.04918032795.72194977862.3191143949

    442.08.5394417405.57.8012.170.2333.32876712336.00512087362.4986999719

    543.010.4498511504.59.7012.830.2539.31168831176.22356783982.5520459526

    606.011.756856256510.8713.670.2641.34146341466.33682573112.614959778

    qmax=17.1821305842

    b=0.0054916022

    Cr(VI)-isotherm (6)

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    Ce (ppm)

    Q (mg Cr/ g biomass)

    Cr(VI)-pH-wo

    6.8345864662

    12.7846153846

    12.0727272727

    16.9390243902

    20.8571428571

    28.4634146341

    30.0491803279

    33.3287671233

    39.3116883117

    41.3414634146

    Ce, mg/L

    Ce/q

    Cr(VI)-pH-w

    ObjectivesEquilibrium isotherm: biosorption of chromate

    Weight of Biomass0.15g

    Volume of solution0.05L

    pH of solution6

    CiCiCe (Set 1)Ce (Set 2)Ce (Avr)Ce (Avr)QQCe/qlnCelnQ

    mg/LmM/Lmg/Lmg/Lmg/Lmmol/Lmg Cr/ g biomassmmol Cr/g biomass

    20.60.418.4018.9018.650.360.650.0128.69-1.0253975725-4.3820266347

    53.01.049.7049.8049.750.961.070.0246.64-0.044233255-3.8867051974

    80.11.573.6074.7074.151.431.980.0437.390.35484635-3.2664647877

    99.51.989.9093.8091.851.772.550.0536.020.5689130931-3.0151503594

    217.04.2204.00205.00204.53.934.170.0849.081.3693242569-2.5241273629

    314.06.0302.00301.00301.55.804.170.0872.361.7575262976-2.5241273629

    427.08.2412.00413.00412.57.934.830.0985.342.0709924872-2.3757073578

    501.09.6487.00489.004889.384.330.08112.622.2390716873-2.4849066498

    551.010.6533.00541.0053710.334.670.09115.072.3347543759-2.4107986776

    qmax=6.5402223676

    b=0.0057635041

    Cr(VI)-pH-w

    0.65

    1.0666666667

    1.9833333333

    2.55

    4.1666666667

    4.1666666667

    4.8333333333

    4.6666666667

    Ce (ppm)

    Q (mg Cr/ g biomass)

    Titration-Sarg

    28.6923076923

    46.640625

    37.3865546218

    36.0196078431

    49.08

    72.36

    85.3448275862

    112.6153846154

    115.0714285714

    Ce (ppm)

    Ce/Q

    kinetic-sarg(pH2)800-1180

    ObjectivepH effects on biosorption of chromium using Sargassum (without pH control)

    Weight of biomass0.15g

    Volume of solution50mL

    pHipHf,1pHf,2pHf,aveCiCf,1Cf,2Cf,aveQ

    mg/Lmg/Lmg/Lmg/Lmg/g

    1.041.071.091.0850.930.930.930.96.67

    2.032.342.342.3452.728.128.228.28.18

    3.014.824.824.8253.849.249.849.51.43

    4.056.136.136.1353.752.152.252.20.52

    4.986.226.256.2455.152.953.753.30.60

    5.976.436.436.4354.251.852.352.10.72

    6.966.946.946.9453.750.653.051.80.63

    7.997.197.187.1954.052.553.453.00.35

    kinetic-sarg(pH2)800-1180

    0

    0

    0

    0

    0

    0

    0

    0

    pHf

    Uptake, q (mg/g)

    kinetic-sarg(pH2) (0.1)

    0

    0

    0

    0

    0

    0

    0

    0

    Initial pH

    Final pH

    kinetic-sarg(pH2)

    ObjectivepH effects on biosorption of chromium using Sargassum (with pH control)

    Weight of biomass0.15g

    Volume of solution50mL

    pHCiCf,1Cf,2Cf,aveQ

    mg/Lmg/Lmg/Lmg/Lmg/g

    1.0450.930.430.230.36.87

    2.0352.725.825.925.858.95

    3.0153.839.239.639.44.80

    4.0553.846.747.246.952.28

    4.9855.150.650.550.551.52

    5.9754.252.352.752.50.57

    6.9653.753.252.953.050.22

    7.995452.853.453.10.30

    kinetic-sarg(pH2)

    0

    0

    0

    0

    0

    0

    0

    0

    pH

    Uptake, q(mg/g)

    kinetic-sarg(pH4)

    10 mL of NaNO3 (0.1M)0.1g sargassum

    0.1 M HNO3

    0.1 M NaOH

    HNO3 addedpH1pH2pHaveNaOH addedpH1pH2pHave

    06.156.166.1606.156.166.16

    0.53.853.733.790.16.336.246.29

    0.73.583.463.520.36.896.836.86

    13.283.153.220.58.668.568.61

    22.542.392.470.79.199.339.26

    32.172.022.10110.2810.3610.32

    41.971.841.91211.111.4811.29

    51.861.711.79311.7611.9211.84

    61.781.631.71412.0312.1112.07

    71.721.571.65512.1612.2312.20

    81.671.521.60612.2512.3112.28

    91.631.471.55

    kinetic-sarg(pH4)

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    Volume of HNO3 added

    pH

    kinetic-sarg(pH6)

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    Volume of NaOH added

    pH

    kinetic study

    ObjectivesKinectic study of chromium

    Weight of Biomass6g

    Volume of solution2L

    pH of solution2

    particle size800-1180mm

    Time (hr)Crtot (Set1)Crtot (Set2)Crtot (Ave)Cr(VI) (Set1)Cr(VI) (Set2)Cr(VI) (Ave)Cr(III) (Set1)Cr(III) (Set2)Cr(III) (Ave)Cr(VI)/Cr(III)

    0.0053.8054.6054.201.0453.5454.8954.221.040.000.000.000.00

    0.2547.1047.3047.200.9144.2645.2644.760.862.842.042.440.0518.34

    0.5043.3044.8044.050.8540.6942.6641.680.802.612.142.380.0517.55

    1.0040.8042.4041.600.8038.7238.1638.440.742.084.243.160.0612.16

    2.0037.4038.9038.150.7332.4233.0232.720.634.985.885.430.106.03

    3.0033.8035.4034.600.6728.2928.6428.470.555.516.766.140.124.64

    4.0032.3034.1033.200.6423.3522.3622.860.448.9511.7410.350.202.21

    6.0029.4030.9030.150.5819.3318.5618.950.3610.0712.3411.210.221.69

    7.0028.0029.7028.850.5516.5116.9916.750.3211.4912.7112.100.231.38

    8.0027.5029.3028.400.5514.3014.2614.280.2713.2015.0414.120.271.01

    10.0025.7027.5026.600.5112.3412.9712.660.2413.3614.5313.950.270.91

    12.0026.0026.5026.250.509.879.269.570.1816.1317.2416.690.320.57

    2425.8025.7025.750.501.651.841.750.0324.1523.8624.010.460.07

    kinetic study

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    Cr(III)

    Cr(VI)

    Cr(total)

    Time (h)

    Chromium Concentration (mmol)

    ionic strength(0.01)

    ObjectivesKinectic study of chromium

    Weight of Biomass6g

    Volume of solution2L

    pH of solution2

    particle size212-500mm

    Time (hr)Crtot (Set1)Crtot (Set2)Crtot (Ave)Cr(VI) (Set1)Cr(VI) (Set2)Cr(VI) (Ave)Cr(III) (Set1)Cr(III) (Set2)Cr(III) (Ave)Cr(VI)/Cr(III)% Removal

    0.005.335.285.310.105.255.305.280.100.000.000.000.0000.00

    0.253.613.653.630.071.871.941.910.041.741.711.730.031.1064.090480678647.65

    0.503.203.193.200.061.361.421.390.031.841.771.810.030.7773.798303487360.03

    1.002.022.002.010.040.610.580.600.011.411.421.420.030.4288.784165881293.74

    2.001.771.791.780.030.110.100.110.001.661.691.680.030.0698.0207351555100.28

    3.001.781.781.780.030.000.000.000.001.781.781.780.030.00100100.28

    4.001.811.791.800.030.000.000.000.001.811.791.800.030.0010099.72

    5.001.821.791.810.030.000.000.000.001.821.791.810.030.0010099.57

    6.001.781.771.780.030.000.000.000.001.781.771.780.030.00100100.43

    7.001.801.821.810.030.000.000.000.001.801.821.810.030.0010099.43

    8.001.781.781.780.030.000.000.000.001.781.781.780.030.00100100.28

    10.001.791.811.800.030.000.000.000.001.791.811.800.030.0010099.72

    12.001.771.791.780.030.000.000.000.001.771.791.780.030.00100100.28

    241.781.801.790.030.000.000.000.001.781.801.790.030.00100100.00

    ionic strength(0.01)

    55.8555.3450

    48.0545.3452.705

    46.943.413.49

    43.939.344.56

    39.633.4756.125

    36.929.0057.895

    34.425.748.66

    32.722.6110.09

    30.9519.3111.64

    29.917.80512.095

    29.115.27513.825

    27.412.8714.53

    2710.53516.465

    26.652.25524.395

    Crtotal

    Cr(VI)

    Cr(III)

    Time (hr)

    Concentration (ppm)

    ionic strength(0.1)

    00

    018.3442622951

    017.5473684211

    012.164556962

    06.0257826888

    04.6397718011

    02.2092798453

    01.6907630522

    01.3842975207

    01.0113314448

    00.9074937253

    00.5732694037

    00.0726931889

    0

    212-500

    800-1180

    Ionic Strength

    01.06432692311.0740384615

    0.05201923080.87201923080.9240384615

    0.06711538460.83480769230.9019230769

    0.08769230770.75653846150.8442307692

    0.11778846150.643750.7615384615

    0.15182692310.55778846150.7096153846

    0.16653846150.4950.6615384615

    0.19403846150.43480769230.6288461538

    0.22384615380.37134615380.5951923077

    0.23259615380.34240384620.575

    0.26586538460.293750.5596153846

    0.27942307690.24750.5269230769

    0.31663461540.20259615380.5192307692

    0.46913461540.04336538460.5125

    Cr(III)

    Cr(VI)

    Cr(total)

    Time(h)

    Cr concentration (mM)

    Cr(iii)-pH-wo

    01.0423076923

    00.9076923077

    00.8471153846

    00.8

    00.7336538462

    00.6653846154

    00.6384615385

    00.5798076923

    00.5548076923

    00.5461538462

    00.5115384615

    00.5048076923

    00.4951923077

    0

    212-500

    800-1180

    Cr(iii)-pH-w

    01.09807692311.0182692308

    01.07596153850.9865384615

    01.06634615380.9846153846

    01.03365384620.9778846154

    01.00288461540.9759615385

    00.98365384620.9673076923

    00.97788461540.9634615385

    00.9750.9576923077

    00.96826923080.9557692308

    00.96634615380.9567307692

    00.968750.9538461538

    00.95769230770.9625

    00.95769230770.9596153846

    pH 2

    pH 4

    pH 6

    Time (h)

    Cr Concentration (mM)

    Cr(precipitation)

    ObjectivesKinectic study of chromium

    Weight of Biomass6g

    Volume of solution2L

    pH of solution2

    particle size212-500mm

    Time (hr)Crtot (Set1)Crtot (Set2)Crtot (Ave)Cr(VI) (Set1)Cr(VI) (Set2)Cr(VI) (Ave)Cr(III) (Set1)Cr(III) (Set2)Cr(III) (Ave)Cr(VI)/Cr(III)% Removal

    0.0055.7056.0055.851.0754.6956.0055.351.060.000.000.000.0000.00

    0.2548.2047.9048.050.9244.9545.7445.350.873.252.162.710.0516.7618.809310653526.71

    0.5046.8047.0046.900.9043.3543.4743.410.833.453.533.490.0712.4422.273948075230.65

    1.0044.7043.1043.900.8440.2838.4039.340.764.424.704.560.098.6329.561324977640.92

    2.0040.0039.2039.600.7633.7533.2033.480.646.256.006.130.125.4740.062667860355.65

    3.0036.9036.9036.900.7129.0828.9329.010.567.827.977.900.153.6748.066248880964.90

    4.0034.5034.3034.400.6625.7425.7425.740.508.768.568.660.172.9753.912264995573.46

    5.0032.7032.7032.700.6323.0822.1422.610.439.6210.5610.090.192.2459.516562220279.28

    6.0031.0030.9030.950.6019.1519.4719.310.3711.8511.4311.640.221.6665.425246195285.27

    7.0030.0029.8029.900.5817.9417.6717.810.3412.0612.1312.100.231.4768.119964189888.87

    8.0029.1029.1029.100.5615.6714.8815.280.2913.4314.2213.830.271.1072.649955237291.61

    10.0027.4027.4027.400.5312.9912.7512.870.2514.4114.6514.530.280.8976.956132497897.43

    12.0026.9027.1027.000.5210.7110.3610.540.2016.1916.7416.470.320.6481.136974037698.80

    2426.8026.5026.650.512.202.312.260.0424.6024.1924.400.470.0995.9623992838100.00

    Cr(precipitation)

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    Crtotal

    Cr(VI)

    Cr(III)

    Time (hr)

    Concentration (ppm)

    Cr(III) Isotherm

    00

    018.3442622951

    017.5473684211

    012.164556962

    06.0257826888

    04.6397718011

    02.2092798453

    01.6907630522

    01.3842975207

    01.0113314448

    00.9074937253

    00.5732694037

    00.0726931889

    0

    212-500

    800-1180

    Time (h)

    Cr(VI)/Cr(III)

    kinetic-Cr(III)

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    Cr(III)

    Cr(VI)

    Cr(total)

    Time(h)

    Cr concentration (mM)

    TOC

    01.0423076923

    00.9076923077

    00.8471153846

    00.8

    00.7336538462

    00.6653846154

    00.6384615385

    00.5798076923

    00.5548076923

    00.5461538462

    00.5115384615

    00.5048076923

    00.4951923077

    0

    212-500

    800-1180

    Time (h)

    Chromium Concentration (mmol)

    TOC(Blank)

    01.09807692311.0182692308

    01.07596153850.9865384615

    01.06634615380.9846153846

    01.03365384620.9778846154

    01.00288461540.9759615385

    00.98365384620.9673076923

    00.97788461540.9634615385

    00.9750.9576923077

    00.96826923080.9557692308

    00.96634615380.9567307692

    00.968750.9538461538

    00.95769230770.9625

    00.95769230770.9596153846

    pH 2

    pH 4

    pH 6

    Time (h)

    Cr Concentration (mM)

    Cr(VI)-pH-wo (0.25mM)

    ObjectivesKinectic study of chromium

    Weight of Biomass6g

    Volume of solution2L

    pH of solution4

    Time (hr)Crtot (Set1)Crtot (Set2)Crtot (Ave)Cr(VI) (Set1)Cr(VI) (Set2)Cr(VI) (Ave)Cr(III) (Set1)Cr(III) (Set2)Cr(III) (Ave)

    0.0057.2057.0057.101.1057.9555.8856.921.090.000.000.000.000

    0.2555.9056.0055.951.0856.6855.6056.141.08-0.780.400.000.0015.7534246575

    0.5055.6055.3055.451.0756.3055.2055.751.07-0.700.100.000.0022.602739726

    1.0053.8053.7053.751.0354.1452.9953.571.03-0.340.710.180.0045.8904109589

    2.0052.0052.3052.151.0052.8851.0751.981.00-0.881.230.170.0067.8082191781

    3.0051.0051.3051.150.9852.2450.9351.590.99-1.240.370.000.0081.5068493151

    4.0050.9050.8050.850.9851.6150.6551.130.98-0.710.150.000.0085.6164383562

    5.0050.6050.8050.700.9851.2349.0050.120.96-0.631.800.590.0187.6712328767

    6.0050.3050.4050.350.9750.3448.5949.470.95-0.041.810.880.0292.4657534247

    7.0050.2050.3050.250.9749.5848.4549.020.940.621.851.240.0293.8356164384

    8.0050.3550.4050.380.9749.2048.0448.620.941.152.361.760.0392.1232876712

    10.0049.6050.0049.800.9648.9447.6248.280.930.662.381.520.03100

    12.0049.5050.1049.800.9649.0747.6248.350.930.432.481.460.03100

    Cr(VI)-pH-wo (0.25mM)

    57.156.9150

    55.9556.14-0.19

    55.4555.75-0.3

    53.7553.5650.185

    52.1551.9750.175

    51.1551.585-0.435

    50.8551.13-0.28

    50.750.1150.585

    50.3549.4650.885

    50.2549.0151.235

    50.7548.622.13

    49.848.281.52

    49.848.3451.455

    Crtotal

    Cr(VI)

    Cr(III)

    Time (hr)

    Concentration (ppm)

    Cr(VI)-pH-wo (0.5mM)

    ObjectivesKinectic study of chromium

    Weight of Biomass6g

    Volume of solution2L

    pH of solution6

    Time (hr)Crtot (Set1)Crtot (Set2)Crtot (Ave)Cr(VI) (Set1)Cr(VI) (Set2)Cr(VI) (Ave)Cr(III) (Set1)Cr(III) (Set2)Cr(III) (Ave)

    0.0053.0052.9052.951.0254.0654.5254.291.040.000.000.000.000.00

    0.2552.0050.6051.300.9950.5653.3551.961.001.44-2.750.000.0052.38

    0.5050.7051.1051.200.9848.4853.7451.110.982.22-2.640.000.0055.56

    1.0050.9050.8050.850.9849.1352.6950.910.981.77-1.890.000.0066.67

    2.0050.8050.7050.750.9850.1752.9551.560.990.63-2.250.000.0069.84

    3.0050.6050.5050.300.9751.9951.7851.891.00-1.39-1.280.000.0084.13

    4.0050.3049.9050.100.9649.0052.1750.590.971.30-2.270.000.0090.48

    5.0050.0049.6049.800.9649.5250.9950.260.970.48-1.390.000.00100.00

    6.0049.5049.9049.700.9649.5250.8750.200.97-0.02-0.970.000.00103.17

    7.0049.9049.6049.750.9651.8651.3951.630.99-1.96-1.790.000.00101.59

    8.0049.7049.5049.600.9551.6051.2651.430.99-1.90-1.760.000.00106.35

    10.0050.2049.9050.050.9651.2150.9951.100.98-1.01-1.090.000.0092.06

    12.0050.0049.8049.900.9651.3350.9951.160.98-1.33-1.190.000.0096.83

    Cr(VI)-pH-wo (0.5mM)

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    Crtotal

    Cr(VI)

    Cr(III)

    Time (hr)

    Concentration (ppm)

    Cr(VI)-pH-wo (1mM)

    ObjectivesKinectic study of chromium

    Weight of Biomass6g

    Volume of solution2L

    pH of solution2

    Time (hr)Crtot (Set1)Crtot (Set2)Crtot (Ave)Cr(VI) (Set1)Cr(VI) (Set2)Cr(VI) (Ave)Cr(III) (Set1)Cr(III) (Set2)Cr(III) (Ave)Cr(VI)/Cr(III)

    0.0055.7056.0055.8554.6956.0055.350.000.000.00

    0.2548.2047.9048.0544.9545.7445.353.252.162.7116.76

    0.5046.8047.0046.9043.3543.4743.413.453.533.4912.44

    1.0044.7043.1043.9040.2838.4039.344.424.704.568.63

    2.0040.0039.2039.6033.7533.2033.486.256.006.135.47

    3.0036.9036.9036.9029.0828.9329.017.827.977.903.67

    4.0034.5034.3034.4025.7425.7425.748.768.568.662.97

    5.0032.7032.7032.7023.0822.1422.619.6210.5610.092.24

    6.0031.0030.9030.9519.1519.4719.3111.8511.4311.641.66

    7.0030.0029.8029.9017.9417.6717.8112.0612.1312.101.47

    8.0029.1029.1029.1015.6714.8815.2813.4314.2213.831.10

    10.0027.4027.4027.4012.9912.7512.8714.4114.6514.530.89

    12.0026.9027.1027.0010.7110.3610.5416.1916.7416.470.64

    2426.8026.5026.652.202.312.2624.6024.1924.400.09

    ObjectivesKinectic study of chromium

    Weight of Biomass6g

    Volume of solution2L

    pH of solution4

    Time (hr)Crtot (Set1)Crtot (Set2)Crtot (Ave)Cr(VI) (Set1)Cr(VI) (Set2)Cr(VI) (Ave)Cr(III) (Set1)Cr(III) (Set2)Cr(III) (Ave)

    0.0057.2057.0057.1057.9555.8856.920.000.000.00

    0.2555.9056.0055.9556.6855.6056.14-0.780.400.00

    0.5055.6055.3055.4556.3055.2055.75-0.700.100.00

    1.0053.8053.7053.7554.1452.9953.57-0.340.710.18

    2.0052.0052.3052.1552.8851.0751.98-0.881.230.17

    3.0051.0051.3051.1552.2450.9351.59-1.240.370.00

    4.0050.9050.8050.8551.6150.6551.13-0.710.150.00

    5.0050.6050.8050.7051.2349.0050.12-0.631.800.59

    6.0050.3050.4050.3550.3448.5949.47-0.041.810.88

    7.0050.2050.3050.2549.5848.4549.020.621.851.24

    8.0050.7050.8050.7549.2048.0448.621.502.762.13

    10.0049.6050.0049.8048.9447.6248.280.662.381.52

    12.0049.5050.1049.8049.0747.6248.350.432.481.46

    ObjectivesKinectic study of chromium

    Weight of Biomass6g

    Volume of solution2L

    pH of solution6

    Time (hr)Crtot (Set1)Crtot (Set2)Crtot (Ave)Cr(VI) (Set1)Cr(VI) (Set2)Cr(VI) (Ave)Cr(III) (Set1)Cr(III) (Set2)Cr(III) (Ave)

    0.0053.0052.9052.9554.0654.5254.290.000.000.00

    0.2552.0050.6051.3050.5653.3551.961.44-2.750.00

    0.5050.7051.1050.9048.4853.7451.112.22-2.640.00

    1.0051.1050.3050.7049.1352.6950.911.97-2.390.00

    2.0052.3050.7051.5050.1752.9551.562.13-2.250.00

    3.0052.1050.5051.3051.9951.7851.890.11-1.280.00

    4.0050.3049.9050.1049.0052.1750.591.30-2.270.00

    5.0050.0049.6049.8049.5250.9950.260.48-1.390.00

    6.0051.2049.9050.5549.5250.8750.201.68-0.970.00

    7.0049.9049.6049.7551.8651.3951.63-1.96-1.790.00

    8.0049.7049.5049.6051.6051.2651.43-1.90-1.760.00

    10.0050.2049.9050.0551.2150.9951.10-1.01-1.090.00

    12.0050.3049.8050.0551.3350.9951.16-1.03-1.190.00

    Cr(VI)-pH-wo (1mM)

    55.8555.3450

    48.0545.3452.705

    46.943.413.49

    43.939.344.56

    39.633.4756.125

    36.929.0057.895

    34.425.748.66

    32.722.6110.09

    30.9519.3111.64

    29.917.80512.095

    29.115.27513.825

    27.412.8714.53

    2710.53516.465

    26.652.25524.395

    Crtotal

    Cr(VI)

    Cr(III)

    Time (h)

    Chromium Concentration (mg/L)

    Cr(VI)-pH-wo (2mM)

    0

    16.7634011091

    12.4383954155

    8.6271929825

    5.4653061224

    3.6738442052

    2.9722863741

    2.2408325074

    1.6589347079

    1.4720959074

    1.1048824593

    0.8857536132

    0.6398420893

    0.0924369748

    Time (h)

    Cr(VI):Cr(III) Ratio

    pH effects

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    Cr(total)

    Cr(VI)

    Cr(III)

    Time (h)

    Chromium Concentration(mg/L)

    effect of cu

    52.9554.290

    51.351.9550

    51.251.110

    50.8550.910

    50.7551.560

    50.351.8850

    50.150.5850

    49.850.2550

    49.750.1950

    49.7551.6250

    49.651.430

    50.0551.10

    49.951.160

    Crtotal

    Cr(VI)

    Cr(III)

    Time (h)

    Chromium Concentration (mg/L)

    ObjectivesKinectic study of chromium

    Weight of Biomass6g

    Volume of solution2L

    pH of solution2

    Ionic Strength0.01MNaNO3

    Time (hr)Crtot (Set1)Crtot (Set2)Crtot (Ave)Cr(VI) (Set1)Cr(VI) (Set2)Cr(VI) (Ave)Cr(III) (Set1)Cr(III) (Set2)Cr(III) (Ave)

    0.0054.5055.5055.0054.7154.2954.500.000.000.00

    0.2548.1048.2048.1545.1245.2645.192.982.942.96

    0.5047.5047.7047.6044.5447.6046.072.960.101.53

    1.0043.8044.6044.2039.2439.5339.394.565.074.82

    2.0039.6041.2040.4033.2334.2333.736.376.976.67

    3.0036.7038.4037.5529.3629.7929.587.348.617.98

    4.0034.8036.0035.4025.9226.0726.008.889.939.41

    5.0033.6034.2033.9023.3523.3523.3510.2510.8510.55

    6.0032.2032.4032.3020.4820.4820.4811.7211.9211.82

    7.0030.7031.7031.2018.4818.7618.6212.2212.9412.58

    8.0029.9029.5029.7016.7616.6116.6913.1412.8913.02

    10.0027.9027.6027.7512.8912.4612.6815.0115.1415.08

    12.0027.6027.4027.5010.1710.3110.2417.4317.0917.26

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    Cr(total)

    Cr(VI)

    Cr(III)

    Time (hr)

    Concentration (ppm)

    ObjectivesKinectic study of chromium

    Weight of Biomass6g

    Volume of solution2L

    pH of solution2

    Ionic Strength0.1MNaNO3

    Time (hr)Crtot (Set1)Crtot (Set2)Crtot (Ave)Cr(VI) (Set1)Cr(VI) (Set2)Cr(VI) (Ave)Cr(III) (Set1)Cr(III) (Set2)Cr(III) (Ave)

    0.0050.4050.4050.4051.1551.2751.210.000.000.00

    0.2545.9045.1045.5043.2043.4443.322.701.662.18

    0.5045.7045.1045.4041.7342.2241.983.972.883.43

    1.0042.8042.1042.4537.3237.3237.325.484.785.13

    2.0039.5039.2039.3532.4332.9232.687.076.286.68

    3.0038.0037.9037.9529.8630.1029.988.147.807.97

    4.0035.8035.5035.6526.9225.8226.378.889.689.28

    5.0034.6034.9034.7524.5024.3724.4410.1010.5310.32

    6.0033.3034.1033.7021.9122.0321.9711.3912.0711.73

    7.0032.0032.0032.0020.4320.5620.5011.5711.4411.51

    8.0030.9031.2031.0516.0016.0016.0014.9015.2015.05

    10.0030.5030.3030.4013.9113.6613.7916.5916.6416.62

    12.0030.3030.1030.2011.5711.5411.5618.7318.5618.65

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    Cr(total)

    Cr(VI)

    Cr(III)

    Time (hr)

    Concentration (ppm)

    Time (h)Ionic StrengthIonic StrengthIonic Strength

    00.01M0.1M

    0.0055.855550.40

    0.2548.0548.1545.50

    0.5046.947.645.40

    1.0043.944.242.45

    2.0039.640.439.35

    3.0036.937.5537.95

    4.0034.435.435.65

    5.0032.733.934.75

    6.0030.9532.333.70

    7.0029.931.232.00

    8.0029.129.731.05

    10.0027.427.7530.40

    12.002727.530.20

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    0

    0.01M

    0.1M

    Time (h)

    concentration (ppm)

    ObjectivepH effects on biosorption of chromium(III) using Sargassum (without pH control)

    Weight of biomass0.15g

    Volume of solution50mL

    pHipHf,1pHf,2pHf,aveCiCf,1Cf,2Cf,aveQ%

    mg/Lmg/Lmg/Lmg/Lmg/gRemoval

    1.051.071.081.0850.144.3043.5043.902.0712.375249501

    2.022.142.182.1649.333.5033.9033.705.2031.6430020284

    2.964.134.144.1452.74.774.794.7815.9790.9297912713

    3.964.874.854.8650.42.712.742.7315.8994.5932539683

    4.505.425.405.4151.22.872.752.8116.1394.51171875

    5.005.895.915.9049.22.822.742.7815.4794.3495934959

    5.486.466.456.4649.43.113.183.1515.4293.6336032389

    0

    0

    0

    0

    0

    0

    0

    0

    Initial pH

    Final pH

    0

    0

    0

    0

    0

    0

    0

    pH

    Metal Removal percentage,%

    6.61666666670

    8.63333333330

    9.06666666670

    8.68333333330

    5.21666666670

    1.51666666670

    1.58333333330

    1.1833333333

    1.3

    0.7833333333

    0.85

    0.6166666667

    Cr3+

    CrO4-

    Final pH

    q, mg/g

    0

    0

    0

    0

    0

    0

    0

    Final pH

    q, mg/g

    ObjectivepH effects on biosorption of chromium(III) using Sargassum (with pH control)

    Weight of biomass0.15g

    Volume of solution50mL

    pHCiCf,1Cf,2Cf,aveQ%

    mg/Lmg/Lmg/Lmg/Lmg/gremoval

    1.0550.144.242.443.32.2713.57

    2.0249.336.235.8364.4326.98

    2.9652.715.715.115.412.4370.78

    3.9650.43.333.463.39515.6793.26

    4.5051.23.513.323.41515.9393.33

    5.0049.22.92.922.9115.4394.09

    5.4849.42.112.062.08515.7795.78

    pHipHCiCiCf,aveCf,ave

    mg/LmMmg/LmM

    1.051.0550.10.9643.300.83

    2.022.0249.30.9536.000.69

    2.962.9652.71.0115.400.30

    3.963.9650.40.973.400.07

    4.504.5051.20.983.420.07

    5.005.0049.20.952.910.06

    5.485.4849.40.952.090.04

    1.051.0850.10.9643.900.84

    2.022.1649.30.9533.700.65

    2.964.1452.71.014.780.09

    3.964.8650.40.972.730.05

    4.505.4151.20.982.810.05

    5.005.9049.20.952.780.05

    5.486.4649.40.953.150.06

    0

    0

    0

    0

    0

    0

    0

    pH

    Metal removal percentage,%

    pHCiCf% PrecipitationCf% Precipitation

    (acidified before filtered)(acidified after filtered)

    4.0052.751.81.7151.62.09

    4.5052.749.95.3150.63.98

    5.0052.751.42.4751.13.04

    5.5052.750.34.5550.14.93

    6.0052.744.216.134.0792.28

    ObjectivesEquilibrium isotherm: biosorption of chromate

    Weight of Biomass0.15gSargassum

    Volume of solution0.05L

    pH of solution4-4.3

    CiCiCe (Set 1)Ce (Set 2)Ce (Avr)Ce (Avr)QQCe/qlnCelnQ

    mg/LmMmg/Lmg/Lmg/Lmmol/Lmg Cr/ gmmol Cr/ g

    20.000.381.631.601.620.036.130.120.2635300517-3.4719087619-2.1383208925

    40.600.782.382.762.570.0512.680.240.2027346831-3.0073378197-1.4114806853

    62.201.203.994.534.260.0819.310.370.2205730066-2.5019745583-0.9904480149

    77.801.507.307.387.340.1423.490.450.3125177406-1.957904876-0.7948108343

    147.002.8350.0051.0050.500.9732.170.621.5699481865-0.0292703823-0.4803129989

    194.503.7481.0081.0081.001.5637.830.732.1409691630.4432054361-0.3180531703

    236.504.55121.50121.50121.502.3438.330.743.16956521740.8486705442-0.3049238789

    280.505.39162.50161.50162.003.1239.500.764.10126582281.1363526167-0.2749430467

    5.3942307692

    Qmax=0.79mmol/g

    b=7.11L/mmol

    n=3.10

    K=0.61

    0

    0

    0

    0

    0

    0

    0

    0

    Ce (mmol/L)

    Q (mmol Cr/g)

    0.2635300517

    0.2027346831

    0.2205730066

    0.3125177406

    1.5699481865

    2.140969163

    3.1695652174

    4.1012658228

    Ce (mmol/L)

    Ce/Q

    -2.1383208925

    -1.4114806853

    -0.9904480149

    -0.7948108343

    -0.4803129989

    -0.3180531703

    -0.3049238789

    -0.2749430467

    LnCe

    LnQ

    ObjectivesKinectic study of chromium(III)

    Weight of Biomass6gSargassum

    Volume of solution2L

    pH of solution4

    Time (hr)Cr(III)(set1)Cr(III) (set2)Cr(III) (ave)Cr(III) (ave) (mmol/L)%Removal(ave)

    0.0050.7050.250.450.97

    0.0816.5016.416.450.3267.390.7411444142

    0.1711.9011.911.900.2376.410.8403269755

    0.339.199.179.180.1881.800.8996185286

    0.508.218.558.380.1683.390.9170572207

    0.757.767.627.690.1584.760.9320980926

    1.007.607.517.560.1585.020.9350408719

    2.006.876.756.810.1386.500.951280654

    4.006.206.026.110.1287.890.9665395095

    6.005.715.665.690.1188.730.9758038147

    8.005.124.975.050.1090.000.9897547684

    12.004.304.614.460.0991.171.0026158038

    24.004.624.534.580.0990.931

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    time(h)

    concentration(mg/g)

    ObjectiveTo determine the TOC content in solution after adsorption

    Weight of Biomass0.15gSargassum

    Volume of solution0.05LCr(VI) solution

    pH of the solution2

    ConcentrationTOCiTOCf

    of Chromium

    mg/Lmg/Lmg/L

    1300.201390.4

    2600.201397.57

    5200.2013105.4

    ObjectiveDetermination of the TOC content in the solution

    Weight of Biomass0.15gSargassum

    Volume of solution0.05LDI water

    pHi(1)pHi(2)pHi(ave)pHf(1)pHf(2)pHf(ave)TOC(1)TOC(2)TOC(ave)TOC(mg/g)%leached out

    0.981.011.001.030.890.9683.2684.0483.6527.882.79

    1.511.531.521.461.411.4477.4977.9077.7025.902.59

    2.002.042.022.162.132.1576.7677.9477.3525.782.58

    2.552.532.543.233.093.1680.1776.6078.3926.132.61

    2.923.062.994.034.714.3783.8284.5884.2028.072.81

    4.034.064.056.436.696.5696.6898.1697.4232.473.25

    5.035.085.066.646.776.7195.0996.1595.6231.873.19

    5.955.945.956.486.786.6390.3396.7593.5431.183.12

    6.856.856.856.676.806.7495.4899.1597.3232.443.24

    8.088.088.086.246.406.3291.6993.7592.7230.913.09

    83.65

    77.695

    77.35

    78.385

    84.2

    97.42

    95.62

    93.54

    97.315

    92.72

    pHf

    TOC

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    pH Initial

    pH Final

    ObjectivepH effects on biosorption of chromium using Sargassum (without pH control)

    Weight of biomass0.15g

    Volume of solution50mL0.25mM

    pHipHf,1pHf,2pHf,aveCiCiCf,1Cf,2Cf,aveCf,aveQ% Crtotal

    mg/LmMmg/Lmg/Lmg/LmMmg/gRemoval

    0.951.051.071.0612.60.246.907.37.10.141.8343.61

    1.541.511.521.5213.60.265.105.25.20.102.8262.13

    1.972.062.072.0713.70.263.913.93.90.073.2771.61

    2.503.223.243.2313.40.266.766.36.50.132.2951.16

    3.054.654.524.5913.40.269.559.79.60.181.2628.25

    3.535.915.915.9113.40.2611.2011.311.30.220.7216.04

    4.036.296.276.2813.40.2611.4011.311.40.220.6815.30

    4.966.416.396.4013.20.2511.5011.411.50.220.5813.26

    6.056.516.586.5513.40.2611.8011.711.80.230.5512.31

    6.966.776.776.7713.10.2512.0011.811.90.230.409.16

    8.056.836.786.8113.20.2512.1011.912.00.230.409.09

    pHf,aveCr(VI)iCr(VI)f,1Cr(VI)f,2Cr(VI)f,aveCr(VI)f,aveCr(III)f,1Cr(III)f,2Cr(III)f,ave% Cr(VI)

    mg/Lmg/Lmg/Lmg/LmMmg/Lmg/Lmg/LRemoval

    1.0612.780.000.000.000.006.907.317.11100.00

    1.5213.450.000.000.000.005.105.205.15100.00

    2.0713.360.000.000.000.003.913.873.89100.00

    3.2312.764.704.544.620.092.061.791.9363.79

    4.5912.839.019.169.090.170.540.520.5329.19

    5.9112.7910.019.969.990.191.191.341.2721.93

    6.2812.929.8910.1710.030.191.511.131.3222.37

    6.4012.8610.329.9510.140.191.181.451.3221.19

    6.5512.7510.2310.3410.290.201.571.361.4719.33

    6.7712.9310.1910.3910.290.201.811.411.6120.42

    6.8112.7310.4110.6010.510.201.691.301.5017.48

    pHf,aveTOC1TOC2TOCaveTOCave%leached

    mg/Lmg/Lmg/Lmg/gout

    1.0695.3496.5095.9231.973.20

    1.5286.5487.1186.8328.942.89

    2.0784.9284.1784.5528.182.82

    3.2396.2786.2591.2630.423.04

    4.5991.6991.4191.5530.523.05

    5.9199.9195.1297.5232.513.25

    6.2897.4598.0797.7632.593.26

    6.4098.1096.7497.4232.473.25

    6.5597.85100.9099.3833.133.31

    6.77101.30102.30101.8033.933.39

    6.81101.0098.7699.8833.293.33

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    pHf

    Uptake, q (mg/g)

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    Initial pH

    Final pH

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    Cr(total)

    Cr(VI)

    Cr(III)

    pHf

    Concentration of Cr (mg/l)

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    pHf

    TOC (mg/l)

    ObjectivepH effects on biosorption of chromium using Sargassum (without pH control)

    Weight of biomass0.15g

    Volume of solution50mL

    pHi,1pHi,2pHi,avepHf,1pHf,2pHf,ave

    1.051.041.051.011.021.02

    1.481.521.501.461.511.49

    2.012.032.022.162.132.15

    2.542.512.533.483.453.47

    3.013.043.034.804.754.78

    3.533.493.515.945.905.92

    3.954.033.996.146.196.17

    5.004.995.006.326.286.30

    6.046.046.046.566.516.54

    7.076.977.026.926.876.90

    8.068.028.047.077.037.05

    pHf,aveCi,1Ci,2Ci,aveCi,aveCf,1Cf,2Cf,aveCf,aveQ% Crtotal

    mg/Lmg/Lmg/LmMmg/Lmg/Lmg/LmMmg/gRemoval

    1.0225.8026.2026.000.5014.0014.2014.10.273.9745.35

    1.4927.8027.5027.650.5311.7011.5011.60.225.3558.27

    2.1528.0027.5027.750.5310.8010.2010.50.205.7562.50

    3.4726.3026.7026.500.5116.9016.2016.60.323.3237.07

    4.7827.5027.2027.350.5322.3021.9022.10.431.7519.64

    5.9225.7026.8026.250.5022.2022.3022.30.431.3313.42

    6.1727.0027.8027.400.5321.9023.5022.70.441.5715.93

    6.3027.5026.5027.000.5224.1023.6023.90.461.0513.27

    6.5427.4026.6027.000.5223.3023.8023.60.451.1514.05

    6.9026.7026.6026.650.5123.6024.1023.90.460.9310.67

    7.0525.5026.1025.800.5023.1024.3023.70.460.707.06

    pHf,aveCr(VI)I,1Cr(VI)I,2Cr(VI)I,aveCr(VI)f,1Cr(VI)f,2Cr(VI)f,aveCr(VI)f,aveCr(III)f,1Cr(III)f,2Cr(III)f,ave% Cr(VI)

    mg/Lmg/Lmg/Lmg/Lmg/Lmg/LmMmg/Lmg/Lmg/LRemoval

    1.0226.3526.9226.640.010.010.010.0013.9914.1914.0999.96

    1.4928.1027.9928.050.010.010.010.0011.6911.4911.5999.96

    2.1528.5628.1028.330.030.040.040.0010.7710.1610.4799.88

    3.4727.0226.8926.9615.1414.9815.060.291.761.221.4944.13

    4.7827.6827.1027.3920.8320.7420.790.401.471.161.3224.11

    5.9226.3027.5226.9122.1222.0822.100.430.080.220.1517.87

    6.1727.8927.8327.8622.5122.1022.310.43-0.611.400.3919.94

    6.3029.1028.3828.7422.7722.7922.780.441.330.811.0720.74

    6.5428.6027.9728.2922.3822.6522.520.430.921.151.0420.40

    6.9027.8127.8327.8222.7722.8022.790.440.831.301.0718.10

    7.0526.5927.8327.2122.6422.7922.720.440.461.510.9916.52

    pHf,aveTOC1TOC2TOCaveTOCave%leached

    mg/Lmg/Lmg/Lmg/gout

    1.0288.0789.0288.5529.522.95

    1.4982.4483.5282.9827.662.77

    2.1579.8280.3980.1126.702.67

    3.4777.8077.9677.8825.962.60

    4.7881.8882.0581.9727.322.73

    5.9285.8086.2986.0528.682.87

    6.1785.8986.6686.2828.762.88

    6.3087.6987.0187.3529.122.91

    6.5490.9891.2391.1130.373.04

    6.9090.3791.4990.9330.313.03

    7.0592.7093.2192.9630.993.10

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    pHf

    Uptake, q(mg/g)

    1.015

    1.485

    2.145

    3.465

    4.775

    5.92

    6.165

    6.3

    6.535

    6.895

    7.05

    Initial pH

    Final pH

    14.10.0114.09

    11.60.0111.59

    10.50.03510.465

    16.5515.061.49

    22.120.7851.315

    22.2522.10.15

    22.722.3050.395

    23.8522.781.07

    23.5522.5151.035

    23.8522.7851.065

    23.722.7150.985

    Cr(total)

    Cr(VI)

    Cr(III)

    pHf

    Cr Concentration (mg/l)

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    pHf

    TOC (mg/l)

    ObjectivepH effects on biosorption of chromium using Sargassum (without pH control)

    Weight of biomass0.15g

    Volume of solution50mL1mM

    pHipHf,1pHf,2pHf,aveCiCiCf,1Cf,2Cf,aveCf,aveQ% Crtotal

    mg/LmMmg/Lmg/Lmg/LmMmg/gRemoval

    1.021.121.091.1150.70.9830.830.930.90.596.6239.15

    1.531.541.531.5450.90.9824.825.225.00.488.6350.88

    2.012.012.012.01541.0426.5027.1026.80.529.0750.37

    2.012.312.342.3353.51.0326.528.427.50.538.6848.69

    2.463.343.413.3853.71.0337.538.638.10.735.2229.14

    3.064.924.854.8952.51.0147.348.648.00.921.528.67

    3.465.725.685.7052.31.0147.247.947.60.911.589.08

    4.056.056.086.0752.21.0048.149.248.70.941.186.80

    5.016.156.216.1853.41.0348.950.149.50.951.307.30

    5.996.026.416.2250.80.9846.050.948.50.930.784.63

    7.036.926.946.9351.60.9948.649.549.10.940.854.94

    7.937.127.157.1450.40.9748.648.548.60.930.623.67

    pHf,aveCr(VI)iCr(VI)f,1Cr(VI)f,2Cr(VI)f,aveCr(VI)f,aveCr(III)f,1Cr(III)f,2Cr(III)f,ave% Cr(VI)Ratio

    mg/Lmg/Lmg/Lmg/LmMmg/Lmg/Lmg/LRemovalCr(III):Cr(tot)

    1.1153.560.010.010.010.0030.7930.8930.8499.981.00

    1.5452.170.010.010.010.0024.7925.1924.9999.981.00

    2.0153.859.8710.3610.120.1916.6316.7416.6981.220.62

    2.3351.8011.2911.5011.400.2215.2116.9016.0678.000.58

    3.3853.6033.3734.2833.830.654.134.324.2336.890.11

    4.8953.4946.0447.2546.650.901.261.351.3112.800.03

    5.7051.0548.1747.5847.880.92-0.970.320.006.220.00

    6.0751.9348.8047.8048.300.93-0.701.400.356.990.01

    6.1852.9448.0449.5848.810.940.860.520.697.800.01

    6.2251.0347.1349.2148.170.93-1.131.690.285.600.01

    6.9353.4349.7749.2149.490.95-1.170.290.007.370.00

    7.1452.8048.6448.3148.480.93-0.040.190.078.190.00

    pHf,aveTOC1TOC2TOCaveTOCave%leached

    mg/Lmg/Lmg/Lmg/gout

    1.1193.2292.9893.1031.033.10

    1.5480.3982.6881.5427.182.72

    2.3378.0680.5979.3326.442.64

    3.3883.8685.2584.5628.192.82

    4.8990.5793.5692.0730.693.07

    5.7090.0992.1191.1030.373.04

    6.0790.0091.3390.6730.223.02

    6.1887.2588.9588.1029.372.94

    6.2292.8891.6692.2730.763.08

    6.9393.0094.5893.7931.263.13

    7.1497.1795.3596.2632.093.21

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    pHf

    Uptake, q (mg/g)

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    Initial pH

    Final pH

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    000

    Cr(total)

    Cr(VI)

    Cr(III)

    pHf

    Concentration of Cr (mg/l)

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    pHf

    TOC (mg/l)

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    pHf

    Ratio Cr(III):Cr(total)

    ObjectivepH effects on biosorption of chromium using Sargassum (without pH control)

    Weight of biomass0.15g

    Volume of solution50mL2mM

    pHipHf,1pHf,2pHf,aveCiCiCf,1Cf,2Cf,aveCf,aveQ% Crtotal

    mg/LmMmg/Lmg/Lmg/LmMmg/gRemoval

    1.040.960.980.9797.81.8871.172.071.61.388.7526.84

    1.491.451.461.46102.01.9664.362.563.41.2212.8737.84

    1.952.132.132.13104.02.0059.759.459.61.1514.8242.74

    2.473.243.143.19105.02.0277.675.976.81.489.4226.90

    3.044.784.804.79106.02.0491.790.291.01.755.0214.20

    3.545.65.615.61107.02.0695.793.194.41.824.2011.78

    4.015.725.715.72106.02.0495.492.193.81.804.0811.56

    4.985.845.865.85102.01.9688.988.488.71.704.4513.09

    5.956.246.296.27102.01.9689.587.588.51.704.5013.24

    6.976.946.966.95102.01.9690.790.290.51.743.8511.32

    7.987.147.137.14101.01.9488.491.690.01.733.6710.89

    pHf,aveCr(VI)iCr(VI)f,1Cr(VI)f,2Cr(VI)f,aveCr(VI)f,aveCr(III)f,1Cr(III)f,2Cr(III)f,ave% Cr(VI)

    mg/Lmg/Lmg/Lmg/LmMmg/Lmg/Lmg/LRemoval

    0.97101.380.380.190.290.0170.7271.8171.2799.72

    1.46101.569.579.559.560.1854.7352.9553.8490.59

    2.13101.0031.7331.9131.820.6127.9727.4927.7368.50

    3.19106.4060.6464.7762.711.2116.9611.1314.0541.07

    4.79102.7893.5191.5892.551.780.000.000.009.96

    5.61105.1097.5795.4496.511.860.000.000.008.18

    5.72105.4997.5796.7997.181.870.000.000.007.88

    5.85103.7591.9693.5192.741.780.000.000.0010.62

    6.2799.6989.5189.7089.611.720.000.000.0010.12

    6.9599.8791.9691.9691.961.770.000.000.007.92

    7.14100.2589.7091.0290.361.740.000.000.009.87

    pHf,aveTOC1TOC2TOCaveTOCave%leached

    mg/Lmg/Lmg/Lmg/gout

    0.97124.60124.1124.3541.454.15

    1.46107.90107.3107.6035.873.59

    2.1398.4897.6598.0732.693.27

    3.1987.7589.6288.6929.562.96

    4.7990.1891.2690.7230.243.02

    5.6196.9395.8296.3832.133.21

    5.7293.4794.9294.2031.403.14

    5.8595.4493.4294.4331.483.15

    6.2799.64100.9100.2733.423.34

    6.95105.90106.21106.0635.353.54

    7.14109.70109.1109.4036.473.65

    8.75

    12.8666666667

    14.8166666667

    9.4166666667

    5.0166666667

    4.2

    4.0833333333

    4.45

    4.5

    3.85

    3.6666666667

    pHf

    Uptake, q (mg/g)

    0.97

    1.455

    2.13

    3.19

    4.79

    5.605

    5.715

    5.85

    6.265

    6.95

    7.135

    Initial pH

    Final pH

    71.550.28571.265

    63.49.5653.84

    59.5531.8227.73

    76.7562.70514.045

    90.9592.5450

    94.496.5050

    93.7597.180

    88.6592.7350

    88.589.6050

    90.4591.960

    9090.360

    Cr(total)

    Cr(VI)

    Cr(III)

    pHf

    Concentration of Cr (mg/l)

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    pHf

    TOC (mg/l)

    ObjectivepH effects on biosorption of chromium using Sargassum (without pH control)

    Weight of biomass0.15g

    Volume of solution50mL2mM

    pH change before and after adsorption

    Blank0.25 mM0.50 mM1.00 mM2.00 mM

    pHipHfpHipHfpHipHfpHipHfpHipHf

    0.980.960.951.061.051.021.021.111.040.97

    1.511.441.541.521.501.491.531.541.491.46

    2.002.151.972.072.022.152.012.331.952.13

    2.553.162.503.232.533.472.463.382.473.19

    2.924.373.054.593.034.783.064.893.044.79

    4.036.563.535.913.515.923.465.703.545.61

    5.036.714.036.283.996.174.056.074.015.72

    5.956.634.966.405.006.305.016.184.985.85

    6.856.746.056.556.046.545.996.225.956.27

    8.086.326.966.777.026.907.036.936.976.95

    8.056.818.047.057.937.147.987.14

    pH effects on different initial concentration

    0.25mM0.5mM1mM2mM

    pHfQ% Crtotal% Cr(VI)pHfQ% Crtotal% Cr(VI)pHfQ% Crtotal% Cr(VI)pHfQ% Crtotal% Cr(VI)

    mg/gRemovalRemovalmg/gRemovalRemovalmg/gRemovalRemovalmg/gRemovalRemoval

    1.061.8343.61100.001.023.9745.3599.961.116.6239.1599.980.978.7526.8499.72

    1.522.8262.13100.001.495.3558.2799.961.548.6350.8899.981.4612.8737.8490.59

    2.073.2771.61100.002.155.7562.5099.882.0481.142.1314.8242.7468.50

    3.232.2951.1663.793.473.3237.0744.132.338.6848.6978.003.199.4226.9041.07

    4.591.2628.2529.194.781.7519.6424.113.385.2229.1436.894.795.0214.209.96

    5.910.7216.0421.935.921.3313.4217.874.891.528.6712.805.614.2011.788.18

    6.280.6815.3022.376.171.5715.9319.945.701.589.086.225.724.0811.567.88

    6.400.5813.2621.196.301.0513.2720.746.071.186.806.995.854.4513.0910.62

    6.550.5512.3119.336.541.1514.0520.406.181.307.307.806.274.5013.2410.12

    6.770.409.1620.426.900.9310.6718.106.220.784.635.606.953.8511.327.92

    6.810.409.0917.487.050.707.0616.526.930.854.947.377.143.6710.899.87

    7.140.623.678.19

    pH effects on the biosorption of Cr(VI) and Cr(III)

    Cr(VI)Cr(III)

    pHfQ% CrtotalpHfQ% Crtotal

    mg/gRemovalmg/gRemoval

    1.116.6239.151.082.0712.38

    1.548.6350.882.165.2031.64

    2.039.0251.324.1415.9790.93

    2.338.6848.694.8615.8994.59

    3.385.2229.145.4116.1394.51

    4.891.528.675.9015.4794.35

    5.701.589.086.4615.4293.63

    6.071.186.801.052.2713.57

    6.181.307.302.024.4326.98

    6.220.784.632.9612.4370.78

    6.930.854.943.9615.6793.26

    7.140.623.674.5015.9393.33

    7.990.31.675.0015.4394.09

    5.4815.7795.78

    7.995452.853.453.10.301.6666666667

    Initial pH vs Final pH (for biosorption of Cr(VI) and Cr(III))

    Blank1 mMCr(VI)1 mMCr(III)

    pHipHfpHipHfpHipHf

    0.980.961.021.111.051.08

    1.511.441.531.542.022.16

    2.002.152.012.332.964.14

    2.553.162.463.383.964.86

    2.924.373.064.894.505.41

    4.036.563.465.705.005.90

    5.036.714.056.075.486.46

    5.956.635.016.18

    6.856.745.996.22

    8.086.327.036.93

    7.937.14

    pH effects on the organic leaching (as a function of different Cr(VI) concentration)

    Blank0.25mM0.5mM1mM2mM

    pHfTOC% leachedpHfTOC% leachedpHfTOC% leachedpHfTOC% leachedpHfTOC% leached

    mg/Loutmg/Loutmg/Loutmg/Loutmg/Lout

    0.9683.652.791.0695.923.201.0288.552.951.1193.103.100.97124.354.15

    1.4477.702.591.5286.832.891.4982.982.771.5481.542.721.46107.603.59

    2.1577.352.582.0784.552.822.1580.112.672.3379.332.642.1398.073.27

    3.1678.392.613.2391.263.043.4777.882.603.3884.562.823.1988.692.96

    4.3784.202.814.5991.553.054.7881.972.734.8992.073.074.7990.723.02

    6.5697.423.255.9197.523.255.9286.052.875.7091.103.045.6196.383.21

    6.7195.623.196.2897.763.266.1786.282.886.0790.673.025.7294.203.14

    6.6393.543.126.4097.423.256.3087.352.916.1888.102.945.8594.433.15

    6.7497.323.246.5599.383.316.5491.113.046.2292.273.086.27100.273.34

    6.3292.723.096.77101.803.396.9090.933.036.9393.793.136.95106.063.54

    6.8199.883.337.0592.963.107.1496.263.217.14109.403.65

    00000

    00000

    00000

    00000

    00000

    00000

    00000

    00000

    00000

    00000

    0000

    Blank

    13 mg/L

    26 mg/L

    52 mg/L

    104 mg/L

    Initial pH

    Final pH

    0000

    0000

    0000

    0000

    0000

    0000

    0000

    0000

    0000

    0000

    0000

    0

    13 mg/L

    26 mg/L

    52 mg/l

    104 mg/L

    pHf

    % Total Chromium Removal

    0000

    0000

    0000

    0000

    0000

    0000

    0000

    0000

    0000

    0000

    0000

    0

    13 mg/L

    26 mg/L

    52 mg/L

    104 mg/L

    pHf

    % Cr(VI) Removal

    00

    00

    00

    00

    00

    00

    00

    00

    00

    00

    00

    00

    00

    0

    Cr(VI)

    Cr(III)

    pHf

    % Chromium Adsorbed

    % Cr(III) Removal

    000

    000

    000

    000

    000

    000

    000

    00

    00

    00

    0

    Blank

    Cr(VI)

    Cr(III)

    Initial pH

    Final pH

    00000

    00000

    00000

    00000

    00000

    00000

    00000

    00000

    00000

    00000

    0000

    Blank

    13 mg/L

    26 mg/L

    52 mg/L

    104 mg/L

    pHf

    TOC (mg/L)

    1000

    1000

    99.9809451220

    55.05701307130

    23.20503330870

    17.76095082910

    14.97763821490

    14.48452144280

    14.26666666670

    12.31621157150

    7.01788491450

    0

    Padina sp.

    Sargassum sp.

    pHf

    % Cr(VI) Removal

    Objectiveeffects of copper on the biosorption of chromium using Sargassum (without pH control)

    Weight of biomass0.15g

    Volume of solution50mL

    Initial pH6

    pHf[Cri][Crf]% Removal[Cui][Cuf]% Removal

    6.4516.5014.6011.520.000.000.00

    6.9916.4012.7022.5611.202.7175.80

    6.9416.9011.7030.7722.106.7369.55

    7.0116.5011.7029.0933.3010.3069.07

    7.0716.2011.6028.4044.1015.0065.99

    7.0516.209.8039.5154.8015.7071.35

    6.7916.104.8270.06112.0013.6587.81

    6.2916.801.4191.61161.0014.3591.09

    6.2317.001.3192.29167.0017.4089.58

    5.7416.200.3797.74275.0037.5586.35

    5.4616.100.3797.71325.5082.0074.81

    0

    0

    0

    0

    0

    0

    0

    0

    0

    0

    Cu Concentration (mg/L)

    % Cr Removal

  • Metal biosorptive properties: pH effect

    Metal biosorptive properties: ionic strength effect

  • Algae as the biosorbents

    Sheet1

    BiomassMetal ionsReferences

    Ascophyllum spp.Ni, Pb, Cd, Cu1.03-1.43Volesky etal., 2000

    Chlorella sp.Cd0.99Aksu, 2001

    Cladophora sp.Pb0.35Jalali etal., 2002

    Cyclotella sp.Cu0.41Schmitt etal., 2001

    Cymodocea spp.Cu, Zn0.71-0.83Sanchez etal., 1999

    Fucus sp.Pb1.6Volesky, 1994

    Gracilaria sp.Pb0.2-0.26Jalali etal., 2002

    Padina spp.Pb, Cu0.31-1.05Volesky, 1994; Jalali etal., 2002; Kaewsarn, 2002

    Phaeodactylum sp.Cu1.67mg/gSchmitt etal., 2001

    Polysiphonia sp.Pb0.49Jalali etal., 2002

    Porphyridium sp.Cu0.27mg/gSchmitt etal., 2001

    Sargassum spp.Pb, Cu, Cd, Ni0.71-1.99Volesky etal., 1994,2000; Jalali etal., 2002

    Scenedesmus spp.Cu, Cd0.06-0.21Schmitt etal., 2001

    Schizomeris spp.Pb, Cd0.31-0.44Ozer etal., 1999

    Spirulina sp.Cd0.87Rangsayatorn etal., 2002

    Ulva sp.Pb0.61Jalali etal., 2002

    Sheet2

    Ascophyllum nodosumNi1.43[11]

    Ascophyllum. NodosumPb1.27[15]

    Ascophyllum. NodosumCu1.19[15]

    Ascophyllum. NodosumCd1.03[15]

    Chlorella vulgarisCd0.99[38]

    Cladophora glomerataPb0.35[43]

    Cyclotella crypticaCu0.41[36]

    Cymodocea nodosaCu0.83[22]

    Cymodocea nodosaZn0.71[22]

    Durvillaea potatorumPb1.55[15]

    Durvillaea potatorumCu1.31[15]

    DURVILLAEA. POTATORUMCd1.12[29]

    Ecklonia maximaCu1.22[15]

    Ecklonia maximaCd1.15[15]

    Ecklonia radiataPb1.26[15]

    Ecklonia radiataCu1.11[15]

    Ecklonia radiataCd1.04[15]

    Fucus vesiculosusPb1.6[12]

    Gracilaria canaliculataPb0.2[43]

    Gracilaria corticataPb0.26[43]

    Laminaria hyperbolaPb1.35[15]

    Laminaria hyperbolaCu1.22[15]

    Laminaria hyperbolaCd0.82[15]

    Laminaria japonicaCu1.2[15]

    Laminaria japonicaCd1.11[15]

    Lessonia flavicansPb1.45[15]

    Lessonia flavicansCu1.25[15]

    Lessonia flavicansCd1.16[15]

    Lessonia nigresenseCu1.26[15]

    Lessonia nigresenseCd1.1[15]

    Padina gymnosporaPb0.31[12]

    Padina pavoniaPb1.05[43]

    padina sp.Cu0.8[42]

    Phaeodactylum tricornutumCu1.67mg/g[36]

    Polysiphonia violaceaPb0.49[43]

    Porphyridium purpureumCu0.27mg/g[36]

    Sargassum FilipendulaCu0.89[11]

    Sargassum FilipendulaCd0.66[11]

    Sargassum fluitansPb1.28[12]

    Sargassum FluitansCu0.8[11]

    Sargassum FluitansCd0.71[11]

    Sargassum FluitansNi1.99[11]

    Sargassum hystrixPb1.38[43]

    Sargassum natansPb1.13[43]

    Sargassum VulgareCu0.93[11]

    Sargassum VulgareCd0.79[11]

    Sargassum vulgarisPb1.1[12]

    Scenedesmus subspicatusCu0.21[36]

    Scenedesmus subspicatusCd0.06[36]

    Schizomeris leibleiniiPb0.31[40]

    Schizomeris leibleiniiCd0.44[40]

    Spirulina platensisCd0.87[32]

    Ulva lactucaPb0.61[43]

    Sheet3

    Biomassmetal ionsqmax (mmol/g)referencesreferences

    Ascophyllum spp.Ni, Pb, Cd, Cu1.03-1.43[11], [15]Volesky etal., 2000

    Chlorella sp.Cd0.99[38]Aksu, 2001

    Cladophora sp.Pb0.35[43]Jalali etal., 2002

    Cyclotella sp.Cu0.41[36]Schmitt etal., 2001

    Cymodocea spp.Cu, Zn0.71-0.83[22]Sanchez etal., 1999

    Fucus sp.Pb1.6[12]Volesky, 1994

    Gracilaria sp.Pb0.2-0.26[43]Jalali etal., 2002

    Padina spp.Pb, Cu0.31-1.05[12], [42], [43]Volesky, 1994; Jalali etal., 2002; Kaewsarn, 2002

    Phaeodactylum sp.Cu1.67mg/g[36]Schmitt etal., 2001

    Polysiphonia sp.Pb0.49[43]Jalali etal., 2002

    Porphyridium sp.Cu0.27mg/g[36]Schmitt etal., 2001

    Sargassum spp.Pb, Cu, Cd, Ni0.71-1.99[11],[12],[43]Volesky etal., 1994,2000; Jalali etal., 2002

    Scenedesmus spp.Cu, Cd0.06-0.21[36]Schmitt etal., 2001

    Schizomeris spp.Pb, Cd0.31-0.44[40]Ozer etal., 1999

    Spirulina sp.Cd0.87[32]Rangsayatorn etal., 2002

    Ulva sp.Pb0.61[43]Jalali etal., 2002

    Laminaria hyperbolaPb, Cu, Cd0.82-1.35[15]

    Durvillaea potatorumPb1.55[15]

    Durvillaea potatorumCu1.31[15]

    DURVILLAEA. POTATORUMCd1.12[29]

    Ecklonia maximaCu1.22[15]

    Ecklonia maximaCd1.15[15]

    Ecklonia radiataPb1.26[15]

    Ecklonia radiataCu1.11[15]

    Ecklonia radiataCd1.04[15]

    Lessonia flavicansPb1.45[15]

    Lessonia flavicansCu1.25[15]

    Lessonia flavicansCd1.16[15]

    Lessonia nigresenseCu1.26[15]

    Lessonia nigresenseCd1.1[15]

  • Mechanisms of metal biosorptionInstrumental investigations through XPS, FTIR, titration and equilibrium experiments reveal that the biosorption is a complex chemical phenomenon.Depended on the types of bisorbents applied, the metal uptake may be due to:metal surface complex formation (MSCF)ion exchange, and elementary coordination

  • XPS spectra of Pb- and Cu-adsorbed CABIER -O-M-O-

  • XPS AnalysisNote that BE values of 577.2 and 579 represent Cr (III) and Cr (VI)Uptake reduction and MSCF

    Raw PadinaCr(VI): pH 1Cr(VI): pH 2Cr(III): pH 4577.1578.5577.2579.2579.5577.5

    Chart1

    35193526.70235193526.6983519.004

    35413529.23535193529.2283519.007

    35653532.3553518.9413532.3433518.953

    37153536.1593518.8173536.1393518.838

    36663540.43518.293540.3663518.324

    35643545.7023517.8933545.6453517.95

    35903552.2653517.7693552.1723517.862

    35693559.7863517.5753559.6353517.725

    36263568.3963517.4373568.1573517.676

    36473577.8353517.1453577.4593517.52

    36443588.123516.7963587.5393517.377

    36863599.1663516.4543598.2783517.341

    36623610.6743515.9983609.3383517.334

    35323622.6063515.6053620.6233517.589

    35963634.9863515.5623632.0823518.465

    37503647.0513515.3453642.8573519.539

    36853658.2973514.7143652.3263520.685

    36353669.113514.2573660.7253522.642

    36253679.3013513.9323667.6853525.548

    36853688.6743513.6343672.8073529.5

    35923697.0713513.1733675.6923534.552

    36043705.0133512.9613676.613541.365

    36723712.4533512.7173675.2363549.934

    37763719.5643512.2883671.4623560.391

    37263726.6383511.583665.3323572.885

    37383734.543511.0033657.4713588.072

    37133743.5423510.3933648.0053605.93

    38223754.1623509.8483637.363626.65

    37473766.383509.0093625.533649.86

    37863780.883508.373613.3873675.863

    39313797.4163507.6243600.9633704.077

    38483815.5363506.4853588.313733.712

    38133835.5143505.5673576.313764.771

    38223856.6883504.7413565.0563796.374

    39543878.1873503.8883554.6093827.467

    39113898.843502.6783544.7393856.779

    39363918.1323501.5813535.9843883.729

    38703934.9073500.4133528.1663907.155

    38523948.4673499.423521.4963926.391

    39193957.8183498.4723515.7943940.497

    39033962.0593497.3423510.7443948.657

    39013960.9333496.2513506.4793950.705

    39723954.1773495.1643502.8623946.479

    39483941.623493.8823499.5953935.906

    39603923.8153492.6613496.8443919.632

    38223901.1663491.4053494.4253898.146

    39023874.8153490.5173492.6673872.665

    37363845.0213489.413490.923843.511

    39013813.3713488.7483489.7933812.326

    38643779.9863487.643488.3543779.272

    37593746.3133486.6283487.1093745.832

    38063713.4423485.8963486.2153713.122

    38413681.6983485.0353485.2453681.489

    36623651.7073484.0793484.2143651.572

    35683624.5373483.63483.6873624.451

    36373600.2293483.3743483.4283600.175

    36323578.5313482.9613482.9943578.498

    35873559.6493482.563482.5813559.628

    35733543.5973482.2793482.2923543.585

    35903530.1453482.0353482.0433530.138

    35533518.9673481.7453481.753518.962

    35873509.9593481.5543481.5563509.957

    35553502.653481.273481.2723502.649

    34763496.9393481.0723481.0733496.939

    35043492.7023481.0863481.0863492.702

    34903489.413481.0243481.0243489.409

    34813486.971348134813486.971

    Binding Energy (eV)

    p1new

    B.E.(eV)Raw IntensityPeak SumBackgroundPeak 1Peak 2difference

    596.93555

    596.83568

    596.73539

    596.63567

    596.53490

    596.43609

    596.33531

    596.23587

    596.13525

    5963574

    595.93615

    595.83584

    595.73582

    595.63544

    595.53489

    595.43553

    595.33582

    595.23581

    595.13621

    5953541

    594.93575

    594.83637

    594.73539

    594.63592

    594.53644

    594.43595

    594.33599

    594.23615

    594.13522

    5943582

    593.93591

    593.83609

    593.73641

    593.63635

    593.53501

    593.43652

    593.33517

    593.23614

    593.13541

    5933454

    592.93541

    592.83741

    592.73597

    592.63563

    592.53515

    592.43571

    592.33594

    592.23577

    592.13546

    5923576

    591.93584

    591.83563

    591.73552

    591.63591

    591.53440

    591.43559

    591.33587

    591.23462

    591.13619

    5913551

    590.93616

    590.83581

    590.73519

    590.63562

    590.53512

    590.43634

    590.33615

    590.23564

    590.13511

    5903575

    589.93600

    589.83582

    589.73536

    589.63565

    589.53665

    589.43629

    589.33719

    589.23674

    589.13575

    5893730

    588.93724

    588.83609

    588.73630

    588.63580

    588.53737

    588.43657

    588.33621

    588.23710

    588.13653

    5883766

    587.93815

    587.83652

    587.73738

    587.63783

    587.53775

    587.43655

    587.33755

    587.23819

    587.13788

    5873713

    586.93762

    586.83768

    586.73769

    586.63651

    586.53734

    586.43753

    586.33674

    586.23677

    586.13668

    5863682

    585.93676

    585.83704

    585.73623

    585.63639

    585.53524

    585.43546

    585.33577

    585.23629

    585.13608

    5853540

    584.93658

    584.83629

    584.73704

    584.63608

    584.53627

    584.43547

    584.33631

    584.23555

    584.13547

    5843645

    583.93585

    583.83679

    583.73557

    583.63533

    583.53638

    583.43606

    583.33654

    583.23522

    583.13496

    5833597

    582.93590

    582.83575

    582.73543

    582.63603

    582.53687

    582.43618

    582.33624

    582.23642

    582.13584

    5823627

    581.93478

    581.83607

    581.73624

    581.635193526.70235193526.6983519.004-7.702393

    581.535413529.23535193529.2283519.00711.76514

    581.435653532.3553518.9413532.3433518.95332.64526

    581.337153536.1593518.8173536.1393518.838178.8408

    581.236663540.43518.293540.3663518.324125.5996

    581.135643545.7023517.8933545.6453517.9518.29761

    58135903552.2653517.7693552.1723517.86237.73486

    580.935693559.7863517.5753559.6353517.7259.214355

    580.836263568.3963517.4373568.1573517.67657.60376

    580.736473577.8353517.1453577.4593517.5269.16528

    580.636443588.123516.7963587.5393517.37755.87988

    580.536863599.1663516.4543598.2783517.34186.83423

    580.436623610.6743515.9983609.3383517.33451.32642

    580.335323622.6063515.6053620.6233517.589-90.60596

    580.235963634.9863515.5623632.0823518.465-38.98608

    580.137503647.0513515.3453642.8573519.539102.9495

    58036853658.2973514.7143652.3263520.68526.70288

    579.936353669.113514.2573660.7253522.642-34.11011

    579.836253679.3013513.9323667.6853525.548-54.30078

    579.736853688.6743513.6343672.8073529.5-3.673828

    579.635923697.0713513.1733675.6923534.552-105.0706

    579.536043705.0133512.9613676.613541.365-101.0134

    579.436723712.4533512.7173675.2363549.934-40.45264

    579.337763719.5643512.2883671.4623560.39156.43604

    579.237263726.6383511.583665.3323572.885-0.6379395

    579.137383734.543511.0033657.4713588.0723.460449

    57937133743.5423510.3933648.0053605.93-30.54175

    578.938223754.1623509.8483637.363626.6567.83789

    578.837473766.383509.0093625.533649.86-19.38037

    578.737863780.883508.373613.3873675.8635.120117

    578.639313797.4163507.6243600.9633704.077133.5837

    578.538483815.5363506.4853588.313733.71232.46362

    578.438133835.5143505.5673576.313764.771-22.51416

    578.338223856.6883504.7413565.0563796.374-34.68799

    578.239543878.1873503.8883554.6093827.46775.81299

    578.139113898.843502.6783544.7393856.77912.16016

    57839363918.1323501.5813535.9843883.72917.86792

    577.938703934.9073500.4133528.1663907.155-64.90723

    577.838523948.4673499.423521.4963926.391-96.46729

    577.739193957.8183498.4723515.7943940.497-38.81812

    577.639033962.0593497.3423510.7443948.657-59.05908

    577.539013960.9333496.2513506.4793950.705-59.93262

    577.439723954.1773495.1643502.8623946.47917.82251

    577.339483941.623493.8823499.5953935.9066.380127

    577.239603923.8153492.6613496.8443919.63236.18481

    577.138223901.1663491.4053494.4253898.146-79.16602

    57739023874.8153490.5173492.6673872.66527.1853

    576.937363845.0213489.413490.923843.511-109.0212

    576.839013813.3713488.7483489.7933812.32687.62866

    576.738643779.9863487.643488.3543779.27284.01367

    576.637593746.3133486.6283487.1093745.83212.68726

    576.538063713.4423485.8963486.2153713.12292.55811

    576.438413681.6983485.0353485.2453681.489159.302

    576.336623651.7073484.0793484.2143651.57210.29297

    576.235683624.5373483.63483.6873624.451-56.53687

    576.136373600.2293483.3743483.4283600.17536.77051

    57636323578.5313482.9613482.9943578.49853.46875

    575.935873559.6493482.563482.5813559.62827.35107

    575.835733543.5973482.2793482.2923543.58529.40259

    575.735903530.1453482.0353482.0433530.13859.85498

    575.635533518.9673481.7453481.753518.96234.03345

    575.535873509.9593481.5543481.5563509.95777.04053

    575.435553502.653481.273481.2723502.64952.34985

    575.334763496.9393481.0723481.0733496.939-20.93945

    575.235043492.7023481.0863481.0863492.70211.29785

    575.134903489.413481.0243481.0243489.4090.590332

    57534813486.971348134813486.971-5.971191

    574.93500

    574.83503

    574.73471

    574.63492

    574.53452

    574.43473

    574.33455

    574.23404

    574.13485

    5743370

    573.93329

    573.83438

    573.73574

    573.63555

    573.53368

    573.43449

    573.33486

    573.23389

    573.13472

    5733450

    572.93447

    572.83558

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    572.63422

    572.53415

    572.43431

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    572.13321

    5723440

    571.93387

    p1new

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    Binding Energy (eV)

    Chart1

    30983139.00930983098.1213138.888

    31343148.18930983098.1953147.994

    32033158.2423097.6513097.9613157.932

    31263168.83096.633097.1163168.313

    30713181.1763096.3453097.0983180.423

    31383194.9883096.5913097.743193.839

    32313208.8623096.1893097.923207.131

    31573222.2633094.8833097.4513219.695

    31193236.5253094.2813098.0413232.765

    32183251.0193094.0413099.4723245.588

    32663264.1233092.8393100.5733256.39

    32133276.1053091.1613102.0233265.242

    32613287.7583089.9793105.0243272.713

    33383298.0483088.3223108.8723277.498

    32173306.7433085.9023113.593279.054

    33593315.9133084.6313121.4173279.126

    33353323.3323081.9713130.1813275.122

    34413330.9953079.5183141.8183268.695

    33883338.1483076.0143155.4153258.748

    32883346.8823072.993172.8063247.066

    34223358.1923070.9063194.6413234.456

    33823370.3363067.5023218.7973219.042

    35153385.3613064.4543246.8773202.938

    34533401.8293060.0863277.0173184.898

    33833421.6493056.2783310.7153167.211

    35523444.6523053.113347.4053150.358

    34183468.083048.2743384.013132.344

    35563494.0833044.693422.43116.374

    36253519.0993039.7343458.8193100.015

    36423542.6663034.0613492.6773084.049

    35673563.9973028.1673523.1093069.055

    34483582.7353022.9443549.7563055.923

    36073598.0563018.8243571.8193045.061

    35653606.23013.1223585.6143033.709

    35683608.2253007.7733592.2973023.701

    36173603.0873002.3423590.9313014.498

    35943590.0522996.3843580.9043005.532

    35013569.8732990.5913563.0822997.381

    34243543.612985.6433538.6382990.615

    34983511.7772981.3943508.1882984.982

    33733473.8832976.3863471.3282978.941

    34553432.9292972.5413431.1352974.335

    33903388.1922967.8653386.9492969.107

    34143342.3312963.7723341.4822964.621

    33393295.692959.4083295.1182959.98

    32783250.4032955.7293250.0232956.108

    31913207.2672952.6043207.0192952.853

    32343167.3852950.2943167.2242950.455

    31483130.0692947.5433129.9672947.646

    31943096.9422945.63096.8772945.665

    31733066.9682943.1923066.9282943.232

    30753040.7912940.9653040.7672940.989

    30223019.0812939.6663019.0662939.68

    29523001.1762938.8673001.1672938.876

    30122986.9472938.742986.9422938.745

    29652974.822938.032974.8172938.033

    29022965.4542937.7692965.4522937.77

    29502958.6662938.1152958.6652938.116

    29382953.04529382953.0452938

    Binding Energy (eV)

    p2new

    B.E.(eV)Raw IntensityPeak SumBackgroundPeak 1Peak 2difference

    596.93097

    596.83122

    596.73168

    596.63079

    596.53166

    596.43085

    596.33059

    596.23056

    596.13166

    5963145

    595.93128

    595.83105

    595.73058

    595.63141

    595.53111

    595.43088

    595.33114

    595.23083

    595.13013

    5953078

    594.93160

    594.83175

    594.73109

    594.63088

    594.53005

    594.43179

    594.33201

    594.23067

    594.13129

    5943046

    593.93058

    593.83093

    593.73154

    593.63173

    593.53082

    593.43236

    593.33157

    593.23132

    593.13110

    5933108

    592.93147

    592.83211

    592.73267

    592.63187

    592.53109

    592.43059

    592.33090

    592.22990

    592.13150

    5923083

    591.93115

    591.83086

    591.73268

    591.63132

    591.53194

    591.43161

    591.33071

    591.23059

    591.13220

    5913135

    590.93018

    590.83173

    590.73168

    590.63108

    590.53153

    590.43085

    590.33148

    590.23107

    590.13173

    5903147

    589.93061

    589.83162

    589.73134

    589.63186

    589.53116

    589.43215

    589.33222

    589.23185

    589.13157

    5893301

    588.93184

    588.83231

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    588.63229

    588.53175

    588.43266

    588.33286

    588.23347

    588.13275

    5883358

    587.93355

    587.83321

    587.73305

    587.63338

    587.53342

    587.43397

    587.33400

    587.23346

    587.13325

    5873350

    586.93415

    586.83380

    586.73364

    586.63281

    586.53212

    586.43395

    586.33332

    586.23263

    586.13300

    5863248

    585.93280

    585.83176

    585.73299

    585.63157

    585.53117

    585.43221

    585.33228

    585.23124

    585.13176

    5853226

    584.93083

    584.83151

    584.73076

    584.63128

    584.53174

    584.43018

    584.33077

    584.23140

    584.13056

    5843042

    583.93127

    583.83107

    583.73116

    583.63088

    583.53045

    583.43115

    583.33022

    583.23133

    583.13048

    5833043

    582.93093

    582.83086

    582.73081

    582.63121

    582.53153

    582.43176

    582.33100

    582.23061

    582.13115

    5823119

    581.93111

    581.83136

    581.73075

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    581.53111

    581.43143

    581.33099

    581.23218

    581.13184

    5813157

    580.93048

    580.83131

    580.730983139.00930983098.1213138.888-41.00854

    580.631343148.18930983098.1953147.994-14.18945

    580.532033158.2423097.6513097.9613157.93244.75781

    580.431263168.83096.633097.1163168.313-42.79956

    580.330713181.1763096.3453097.0983180.423-110.1758

    580.231383194.9883096.5913097.743193.839-56.98828

    580.132313208.8623096.1893097.923207.13122.13818

    58031573222.2633094.8833097.4513219.695-65.26343

    579.931193236.5253094.2813098.0413232.765-117.5254

    579.832183251.0193094.0413099.4723245.588-33.01904

    579.732663264.1233092.8393100.5733256.391.876953

    579.632133276.1053091.1613102.0233265.242-63.10498

    579.532613287.7583089.9793105.0243272.713-26.75806

    579.433383298.0483088.3223108.8723277.49839.9519

    579.332173306.7433085.9023113.593279.054-89.74268

    579.233593315.9133084.6313121.4173279.12643.08716

    579.133353323.3323081.9713130.1813275.12211.66821

    57934413330.9953079.5183141.8183268.695110.0054

    578.933883338.1483076.0143155.4153258.74849.85156

    578.832883346.8823072.993172.8063247.066-58.88159

    578.734223358.1923070.9063194.6413234.45663.80811

    578.633823370.3363067.5023218.7973219.04211.66357

    578.535153385.3613064.4543246.8773202.938129.6389

    578.434533401.8293060.0863277.0173184.89851.17139

    578.333833421.6493056.2783310.7153167.211-38.64868

    578.235523444.6523053.113347.4053150.358107.3477

    578.134183468.083048.2743384.013132.344-50.07959

    57835563494.0833044.693422.43116.37461.9165

    577.936253519.0993039.7343458.8193100.015105.9006

    577.836423542.6663034.0613492.6773084.04999.33423

    577.735673563.9973028.1673523.1093069.0553.00293

    577.634483582.7353022.9443549.7563055.923-134.7354

    577.536073598.0563018.8243571.8193045.0618.943604

    577.435653606.23013.1223585.6143033.709-41.20044

    577.335683608.2253007.7733592.2973023.701-40.22534

    577.236173603.0873002.3423590.9313014.49813.91333

    577.135943590.0522996.3843580.9043005.5323.948486

    57735013569.8732990.5913563.0822997.381-68.87256

    576.934243543.612985.6433538.6382990.615-119.6096

    576.834983511.7772981.3943508.1882984.982-13.77661

    576.733733473.8832976.3863471.3282978.941-100.8833

    576.634553432.9292972.5413431.1352974.33522.07129

    576.533903388.1922967.8653386.9492969.1071.808105

    576.434143342.3312963.7723341.4822964.62171.6687

    576.333393295.692959.4083295.1182959.9843.31006

    576.232783250.4032955.7293250.0232956.10827.59741

    576.131913207.2672952.6043207.0192952.853-16.26733

    57632343167.3852950.2943167.2242950.45566.61523

    575.931483130.0692947.5433129.9672947.64617.93066

    575.831943096.9422945.63096.8772945.66597.05835

    575.731733066.9682943.1923066.9282943.232106.032

    575.630753040.7912940.9653040.7672940.98934.20874

    575.530223019.0812939.6663019.0662939.682.919434

    575.429523001.1762938.8673001.1672938.876-49.17627

    575.330122986.9472938.742986.9422938.74525.05273

    575.229652974.822938.032974.8172938.033-9.819824

    575.129022965.4542937.7692965.4522937.77-63.45386

    57529502958.6662938.1152958.6652938.116-8.66626

    574.929382953.04529382953.0452938-15.04517

    574.82972

    574.73092

    574.62862

    574.52964

    574.42998

    574.32896

    574.22891

    574.12898

    5742959

    573.92813

    573.82920

    573.72870

    573.62928

    573.52949

    573.42884

    573.32847

    573.22984

    573.12892

    5732963

    572.92945

    572.82936

    572.72905

    572.62863

    572.52928

    572.42895

    572.32867

    572.22919

    572.12983

    5723014

    571.92912

    p2new

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    Binding Energy (eV)

    Chart1

    34543456.95934543454.0033456.956

    34203458.15734543454.0063458.151

    35133460.0413454.2793454.293460.03

    34583461.6713453.7973453.8153461.652

    34073464.3783453.7633453.7943464.347

    34713468.263454.1463454.1983468.208

    35883472.5193454.0083454.0933472.433

    35333476.8613452.9083453.0473476.723

    34793482.8233452.2513452.4723482.602

    35273490.5343452.0323452.383490.186

    35893499.2553451.4173451.9573498.715

    35373508.9383450.2873451.1133508.113

    35893520.553449.5763450.8183519.307

    36373533.1963448.4323450.2753531.353

    35413546.8373446.8843449.5783544.143

    35983562.4853446.1123449.993558.606

    35743578.6923444.8653450.3673573.191

    35793595.8763443.8063451.4963588.186

    36013613.483442.6963453.2853602.892

    36353631.0713441.3973455.7643616.704

    36793648.2033439.8083459.0113629

    35483664.4993437.8453463.1313639.213

    36743681.1353436.9413469.7523648.324

    36803695.773434.9963476.9353653.832

    36853709.2433432.9853485.8073656.421

    37723721.4443430.9173496.4553655.906

    38083731.6693428.1183508.2333651.553

    37613740.3363425.0013521.53643.836

    37633748.1313422.2433536.7483633.626

    37243754.6913419.4473553.3233620.815

    37583760.3383416.9483571.1463606.14

    37153764.4393414.1493589.1333589.456

    37333767.5283411.683607.3323571.875

    37993768.9393409.0433624.5593553.423

    37183768.0723405.8433639.7473534.168

    37003765.8743403.2813653.3793515.776

    37923761.5723400.8463664.3133498.105

    37133754.0153397.6363671.0933480.558

    37333744.4083395.0483674.6773464.78

    37113731.8193392.2753673.9933450.101

    36853716.5883389.6593669.293436.957

    37003698.8523387.2363660.6973425.39

    37033678.4933384.6693648.1433415.02

    37603655.9783382.0573632.1643405.871

    37293631.2843378.9553612.8593397.38

    36353605.6733376.0833591.6113390.144

    35453580.2063373.9583569.6223384.542

    35293555.4063372.5543547.5513380.409

    35893531.2323371.273525.4813377.021

    35053507.5113369.4833503.363373.635

    34133485.8443368.3713482.8883371.327

    34293466.5913368.0053464.5153370.081

    33973449.0673367.5043447.6293368.942

    34663433.7913367.2623432.8093368.244

    34703419.9363366.4523419.2743367.114

    34393407.9863365.6023407.5473366.042

    33653398.10333653397.8153365.288

    Binding Energy (eV)

    Cr(III)pnew

    B.E.(eV)Raw IntensityPeak SumBackgroundPeak 1Peak 2difference

    596.83452

    596.73488

    596.63436

    596.53347

    596.43405

    596.33452

    596.23504

    596.13457

    5963427

    595.93380

    595.83481

    595.73540

    595.63413

    595.53499

    595.43439

    595.33454

    595.23394

    595.13483

    5953429

    594.93524

    594.83382

    594.73440

    594.63447

    594.53441

    594.43477

    594.33435

    594.23362

    594.13423

    5943380

    593.93431

    593.83494

    593.73362

    593.63411

    593.53447

    593.43440

    593.33413

    593.23414

    593.13423

    5933417

    592.93446

    592.83311

    592.73406

    592.63456

    592.53531

    592.43430

    592.33401

    592.23499

    592.13413

    5923539

    591.93484

    591.83469

    591.73419

    591.63394

    591.53506

    591.43411

    591.33449

    591.23503

    591.13465

    5913457

    590.93493

    590.83610

    590.73527

    590.63437

    590.53490

    590.43479

    590.33386

    590.23485

    590.13381

    5903450

    589.93522

    589.83382

    589.73429

    589.63493

    589.53463

    589.43564

    589.33427

    589.23499

    589.13523

    5893507

    588.93517

    588.83397

    588.73502

    588.63584

    588.53731

    588.43560

    588.33564

    588.23612

    588.13570

    5883617

    587.93648

    587.83547

    587.73573

    587.63594

    587.53642

    587.43514

    587.33656

    587.23642

    587.13583

    5873615

    586.93691

    586.83620

    586.73521

    586.63635

    586.53537

    586.43687

    586.33518

    586.23536

    586.13578

    5863668

    585.93443

    585.83567

    585.73492

    585.63451

    585.53467

    585.43510

    585.33412

    585.23533

    585.13447

    5853522

    584.93530

    584.83496

    584.73471

    584.63370

    584.53421

    584.43477

    584.33435

    584.23357

    584.13363

    5843362

    583.93508

    583.83494

    583.73433

    583.63440

    583.53446

    583.43452

    583.33461

    583.23497

    583.13504

    5833444

    582.93411

    582.83449

    582.73471

    582.63521

    582.53398

    582.43392

    582.33436

    582.23458

    582.13488

    5823493

    581.93501

    581.83491

    581.73384

    581.63349

    581.53373

    581.43499

    581.33365

    581.23538

    581.13504

    58134543456.95934543454.0033456.956-2.959473

    580.934203458.15734543454.0063458.151-38.15747

    580.835133460.0413454.2793454.293460.0352.95947

    580.734583461.6713453.7973453.8153461.652-3.670654

    580.634073464.3783453.7633453.7943464.347-57.37769

    580.534713468.263454.1463454.1983468.2082.73999

    580.435883472.5193454.0083454.0933472.433115.4814

    580.335333476.8613452.9083453.0473476.72356.13892

    580.234793482.8233452.2513452.4723482.602-3.823242

    580.135273490.5343452.0323452.383490.18636.46558

    58035893499.2553451.4173451.9573498.71589.74536

    579.935373508.9383450.2873451.1133508.11328.06177

    579.835893520.553449.5763450.8183519.30768.4502

    579.736373533.1963448.4323450.2753531.353103.8037

    579.635413546.8373446.8843449.5783544.143-5.837158

    579.535983562.4853446.1123449.993558.60635.51538

    579.435743578.6923444.8653450.3673573.191-4.692383

    579.335793595.8763443.8063451.4963588.186-16.87598

    579.236013613.483442.6963453.2853602.892-12.48047

    579.136353631.0713441.3973455.7643616.7043.929199

    57936793648.2033439.8083459.011362930.79712

    578.935483664.4993437.8453463.1313639.213-116.499

    578.836743681.1353436.9413469.7523648.324-7.134521

    578.736803695.773434.9963476.9353653.832-15.77002

    578.636853709.2433432.9853485.8073656.421-24.24268

    578.537723721.4443430.9173496.4553655.90650.55615

    578.438083731.6693428.1183508.2333651.55376.3313

    578.337613740.3363425.0013521.53643.83620.66431

    578.237633748.1313422.2433536.7483633.62614.86865

    578.137243754.6913419.4473553.3233620.815-30.69092

    57837583760.3383416.9483571.1463606.14-2.338379

    577.937153764.4393414.1493589.1333589.456-49.43945

    577.837333767.5283411.683607.3323571.875-34.52759

    577.737993768.9393409.0433624.5593553.42330.06055

    577.637183768.0723405.8433639.7473534.168-50.07202

    577.537003765.8743403.2813653.3793515.776-65.87378

    577.437923761.5723400.8463664.3133498.10530.42847

    577.337133754.0153397.6363671.0933480.558-41.01465

    577.237333744.4083395.0483674.6773464.78-11.4082

    577.137113731.8193392.2753673.9933450.101-20.8186

    57736853716.5883389.6593669.293436.957-31.58813

    576.937003698.8523387.2363660.6973425.391.148193

    576.837033678.4933384.6693648.1433415.0224.50659

    576.737603655.9783382.0573632.1643405.871104.0217

    576.637293631.2843378.9553612.8593397.3897.71606

    576.536353605.6733376.0833591.6113390.14429.32739

    576.435453580.2063373.9583569.6223384.542-35.20605

    576.335293555.4063372.5543547.5513380.409-26.40576

    576.235893531.2323371.273525.4813377.02157.76807

    576.135053507.5113369.4833503.363373.635-2.510986

    57634133485.8443368.3713482.8883371.327-72.84375

    575.934293466.5913368.0053464.5153370.081-37.59082

    575.833973449.0673367.5043447.6293368.942-52.06665

    575.734663433.7913367.2623432.8093368.24432.20898

    575.634703419.9363366.4523419.2743367.11450.06445

    575.534393407.9863365.6023407.5473366.04231.01367

    575.433653398.10333653397.8153365.288-33.10327

    575.33379

    575.23437

    575.13360

    5753402

    574.93407

    574.83286

    574.73327

    574.63418

    574.53325

    574.43258

    574.33383

    574.23307

    574.13265

    5743342

    573.93298

    573.83396

    573.73270

    573.63323

    573.53401

    573.43255

    573.33318

    573.23315

    573.13361

    5733314

    572.93357

    572.83404

    572.73315

    572.63361

    572.53349

    572.43362

    572.33330

    572.23322

    572.13394

    5723344

    571.93331

    571.83340

    Cr(III)pnew

    Binding Energy (eV)

    Chart3

    2337

    2337

    2275

    2426

    2359

    2320

    2350

    2360

    2380

    2327

    2351

    2398

    2317

    2257

    2293

    2302

    2381

    2357

    2330

    2307

    2312

    2364

    2281

    2325

    2257

    2382

    2365

    2399

    2269

    2289

    2307

    2388

    2173

    2317

    2260

    2320

    2318

    2306

    2272

    2273

    2302

    2363

    2288

    2402

    2398

    2411

    2344

    2333

    2324

    2326

    2261

    2250

    2308

    2409

    2327

    2327

    2277

    2295

    2313

    2373

    2331

    2338

    2302

    2323

    2416

    2313

    2329

    2294

    2290

    2385

    2315

    2321

    2339

    2266

    2378

    2315

    2338

    2284

    2277

    2315

    2300

    2325

    2244

    2358

    2301

    2372

    2325

    2340

    2314

    2309