ASL Conference 2011

Inside Informal, Outside Stormy

Azra Daud
Winthrop Prof. Carolyn Oldham Dr Suzanne McDonald

OUTLINES

Motivation Aims Introduction Approach Methodology Challenges Outcomes Take home message
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MOTIVATION

DOC controls geochemical and ecological processes in aquatic ecosystems. Quantifying and characterising DOC, including its spatial and temporal variability, is critical to understand its role in these processes. Metal-humic issue can be acute in wetland affected by acid sulfate soils or acid mine drainage, which frequently contain high DOC and metal concentrations under low pH conditions.
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AIMS

Inside:

To determine the variability of DOC reactivity, as indicated by its molecular weight distribution, the extent of oxidation, its functional groups and its aromaticity, under acidic environment To quantify the effects of the variable pH on Fe-DOC and Al-DOC complexations

Outside:

To investigate the hydrological connectivity and its impact on the integrated wetland system

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INTRODUCTION

5.8 x 106 ha in Australia 0.76%

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Potential ASS Actual ASS

INTRODUCTION

ASS are of major environmental concern for many wetlands and is made up of oxidisable sulfidic material, usually pyrite, FeS2 (Green et al., 2006)

Iron is one of the main weathering products of pyrite, Fe2SO4 (Peiffer et al., 1999)

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INTRODUCTION Swan Coastal Plain, 180 km south of Perth, Western Australia ~30 ha Hot dry summers (16 30C) and Cool wet winter (7 17C) Rainfall: ~700 mm Evaporation: ~1500 mm

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INTRODUCTION -Acid sulfate soils -Hydrological connectivity

Evaporation

Precipitation DOM Peatland DOM, Al, Fe, H+ DOM Infiltration

Peatland Subsurface flow Groundwater flow

Fe-DOM Al-DOM

DOM, Al, Fe, H+ DOM, Al, Fe, H+

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Bores
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APPROACH

Inside:

Field measurement : pH, EC, ORP, Temp, depth Laboratory analysis : HPSEC, UV-vis, TOC, cation exchange, fractionation, phenanthroline, ICP-AES

Outside:

Survey work site elevation Collecting meteorological data from BOM, WA

Model:

Damkohler number Water and chemical mass balance Reaction rate

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METHODOLOGY Natural Organic Matter

Humus

Undecomposed Matter

Humin

Humic Substances

DOM

Humic Acid

Fulvic Acid 0.45 m membrane syringe filter

DOC
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METHODOLOGY

Pure Sample
0.45 m filter

Laboratory Analysis

DOC Characterization pH adjustment

Fe Total
Phenanthroline 510 nm

SUVA
254 nm

CE

RF

LOI

SRFA
Without Fe With known Fe
(20 1000 mg/L)

TOC
APHA Method 5310A 5 310C Optimum

SEC
Mw Mn

3 years sampling August 09 July 11 Seasonal High water table Low water table
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CHALLENGES & SOLUTIONS

1. Loss on ignition method was not applicable for [C] measurement (negative reading of [C] TOC analysis). 2. TOC Standard Method 5310A was not consistent, and no similarity as compared to Method 5310C. Optimisation was performed and results were validated (5 months). 3. Results by phenanthroline method were not in the range. Modification was undertaken. Reduce sample volume, 1:10 ratio to standard). 4. Purification of carbon by reverse osmosis did not succeed. Aggregation problem occur, less [C] were measured. (Cation Exchange and Rapid Fractionation).

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OUTCOMES

1. Stable pHs did not affect [FeT] in both surface and ground waters, but varying pHs revealed vice versa. 2. In complexation point of view, from HPSEC results, presence of Fe effects the HMW DOC. (High aromatic, more reactive, easily attract to cations, influenced by ionic strength). 3. In Muddy Lake ground water, [FeT] are much relied on the [DOC]. (Negative relationship, colloids formation, not measured). 4. RF technique revealed a different functional group of organic carbon in Muddy lake (hydrophobic during winter, hydrophilic during summer). 5. From survey work, no connection between seasonal hydrology and the wetland system during dry season, however both were well connected during wet season.
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*Paper 1 & 2
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TAKE HOME MESSAGES

1. Multiple tools analysis provides different view of characterising DOC and provides improved understanding in the variability of DOC characteristics and reactivity. 2. When dealing with waters and organic matter under variable pHs, method validation is very CRUCIAL ! 3. Surface and ground water in an aquatic system do not always exhibit similar behavior spatially and temporally, especially under high variability of DOC, heavy metals and pHs. 4. Results have flagged significant remarks on handling natural waters affected by ASS.

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ACKNOWLEDGEMENT

Funding Malaysian Ministry of Higher Education (Tuition) Universiti Tun Hussein Onn Malaysia (Stipend) Australian Government (Natural Heritage Trust Regional (project 53454) Curtin Water Quality Research Centre (Laboratories) People Adam Lilicrap Bibhash Nath Daniel Boland Laura Ellis SESE postgrads Family

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THANK YOU

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CHALLENGES : [DOC] and [FET]

18 16 14 12 10 8 6 4 2 0 2 4 4.5 pH 40 35 30 25 20 15 10 5 0 1 80 70 60 DOC (mg/L) 50 40 30 20 10 0 2 4 4.5 pH 6 8 1.5 mL 3.0 mL 5.0 mL HTC 3 Bores 5 7 6 8

DOC (mg/L)

1.5 mL 3.0 mL 5.0 mL HTC

DOC (mg/L)

1.5 mL, 3% 3.0 mL, 4% HTC

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RESULTS AND DISCUSSION : PAPER 1 & 2 50 mg/L C from International Humic Substances Society Suwannee River Fulvic Acid with different known concentrations of Fe
1000mg/L Fe 200mg/L Fe 100mg/L Fe 80mg/L Fe 60mg/L Fe

120 100 80 Abs 254nm 60

40mg/L Fe 20mg/L Fe Without Fe

40 20 0 1000

100000

10000 Mw

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RESULTS AND DISCUSSION : PAPER 1 Trends of pH, Fe and DOC across wetland in wet season (2009)
9 8 7 6 5 50 70 60

Fe, DOC (mg/L)

40 30 20 10 0 Bore Bore Bore Bore Bore Bore Bore Bore SWN SWS 1 2 3 4 5 6 7 8

pH

4 3 2 1 0

Sample
Fe

pH

DOC DOC High Temp Catalytic 8.0 31.0 3.4 16.0

Sample

Fe (mg/L) 4.92 0.19 62.14 19.92

pH

Mw at pH 7

SUVA

SUVA Bore 1 values for waters in Bore 3 Bore 1, 3, Bore 5 5 and 7 04, 2012 Sunday, March
Bore 7

Name

Wet Oxidation 8.0 - 19.8 36.5 - 37.2 2.6 - 4.3 18.0 - 20.1

8.1 7.9 3.2 2.9

2492 3074 1379 1670

1.26 1.13 3.46 3.06

0.22 1.44 0.77

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3.04

RESULTS AND DISCUSSION : PAPER 1

120 100 80 Abs 254nm

ii

60 40 20 0 1000
Bore4 pH8.25 N pH2.69

10000
Bore1 pH8.09 Bore6 pH8.48 Bore2 pH8.43 Bore7 pH2.93

Mw
Bore3 pH7.90 Bore8 pH8.22

Bore5 pH3.17 S pH2.76

120 100 80 Abs 254nm

ii

60 40 20 0 1000

10000
Bore1 pH7 Bore6 pH7 Bore2 pH7 Bore7 pH7

Mw Bore3 pH7 Bore8 pH7

Bore4 pH7 N pH7

Bore5 pH7 S pH7

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BACKGROUND

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METHOD: BACKGROUND Physicochemical parameters: pH Loss on ignition Electrical conductivity Temperature Oxidation reduction (redox) potential

Chemical analysis: Fe DOC Al QA/QC: Sample collected Samples were stored on ice, transferred to the laboratory and then stored in the dark at 4oC until analysis. Depth to groundwater (relative to Local Datum) was measured prior to sample collection.

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BACKGROUND

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RESULTS AND DISCUSSION Trends of pH, Fe and DOC across wetland in wet season (2010)
70 60 50 9 8 7 6 5 50 40 30 20 10 0 Bore Bore Bore Bore Bore Bore Bore Bore SWN SWS 1 2 3 4 5 6 7 8 Sampl pH Fe DOC 70 60

Trends of pH, Fe and DOC across wetland in wet season (2009)

9 8 7 6 5

Fe, DOC (mg/L)

Fe, DOC (mg/L)

40 30 20 10 0 Bore Bore Bore Bore Bore Bore Bore Bore SWN SWS 1 2 3 4 5 6 7 8

pH

pH

4 3 2 1 0

4 3 2 1 0

Sample
Fe

pH

DOC

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INTRODUCTION

ASS are of major environmental concern for many wetlands and is made up of oxidisable sulfidic material, usually pyrite, FeS2 (Green et al., 2006)

Iron is one of the main weathering products of pyrite (Peiffer et al., 1999)

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METHODOLOGY Size Exclusion Chromatography (SEC) Chromatographic method (molecules in solution are separated by size) Also known as permeation gel method Use organic solvent as a mobile phase Provide good molar mass distribution for polymers Principles: A very large molecule will elute earlier when mobile phase passed through the column. A small molecule will elute late when the pore- and interparticle volume passed through the column.

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BACKGROUND (dissolved)

Fe(II) + S22(oxidized) (a) (a)

+ O2 SO42- + Fe(II)

FeS2(s) + O2

Releasing additional acidity and new Fe(II)

(fast)

+ O2 (b)
(slow)

(c)

+ FeS2(s)

Fe(III)
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Fe(OH)3 (s)
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(soluble)

BACKGROUND

Natural Organic Matter

Humus

Undecomposed Matter

Humin

Humic Substances

Humic Acid

Fulvic Acid

DOM

0.45 micron filter

DOC

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RESULTS AND DISCUSSION

Sample Name Bore 1 Bore 3 Bore 5 Bore 7 Wet Oxidation 8.0 - 19.8 36.5 - 37.2 2.6 - 4.3 18.0 - 20.1

DOC High Temp Catalytic 8.0 31.0 3.4 16.0

Fe (mg/L)

pH

Mw at pH 7

SUVA

8.1 7.9 3.2 2.9

2492 3074 1379 1670

1.26 1.13 3.46 3.06

0.22 1.44 0.77 3.04

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BACKGROUND

Site Description
Small seasonally inundated wetland in the Minningup Wetland Chain 10 km south of Bunbury Mediterranean type climate (wet and dry) Average annual rainfall : 850 mm (May-Oct) and 130 mm (Nov-Apr) Air temperature : 8.2oC (July) - 27.6oC (Feb) Annual potential evaporation : 1400 -1600 mm

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