““Napoleon's hair and old lace: Napoleon's hair and old lace: proactive water managementproactive water management””

Patrick LouchouarnPatrick Louchouarn

Columbia University - MPA ESSPMColumbia University - MPA ESSPM

““How is it possible to find meaning in a finite world,How is it possible to find meaning in a finite world,given my waist and shirt size?given my waist and shirt size?””

Woody AllenWoody Allen

OutlineOutline Arsenic: From South Texas to Arsenic: From South Texas to

Central Arizona (a case for water Central Arizona (a case for water management)management)

1)1) Identification of metal sources to Identification of metal sources to surface water systemssurface water systems

2)2) Long term metal cyclingLong term metal cycling

3)3) What’s cooking…What’s cooking…

Napoleon’s hair and an old lace…Napoleon’s hair and an old lace…

““The level of arsenic found in The level of arsenic found in Napoleon's hair is higher than 10-Napoleon's hair is higher than 10-40 times the normal amounts and 40 times the normal amounts and

is an unmistakable sign of is an unmistakable sign of poisoning”poisoning”

Pascal Kintz,Pascal Kintz,

Strasbourg Forensic InstituteStrasbourg Forensic Institute

Arsenic in Bangladesh Drinking WaterArsenic in Bangladesh Drinking WaterIt’s pretty bad…...It’s pretty bad…...

““If I die, I will die, but I will not fetch water from another If I die, I will die, but I will not fetch water from another man’s house”man’s house”

Bangladeshi villagerBangladeshi villager

Arsenic in BangladeshArsenic in Bangladesh 95% people use groundwater 95% people use groundwater

as drinking source from as drinking source from alluvial and deltaic aquifersalluvial and deltaic aquifers

““Naturally”Naturally” occurring Arsenic occurring Arsenic contamination contamination

~ 175, 000 people suffer from ~ 175, 000 people suffer from chronic As poisoningchronic As poisoning

Symptoms of Chronic ArsenicosisSymptoms of Chronic Arsenicosis

Dealing with chronic As poisoningDealing with chronic As poisoning

Arsenic in Texas Drinking WaterArsenic in Texas Drinking WaterIt’s not so bad…...It’s not so bad…...

““If it donna kill ya, it probably ain’t bad for ya”If it donna kill ya, it probably ain’t bad for ya”

Texas villagerTexas villager

Finalized EPA Drinking Standard for ArsenicFinalized EPA Drinking Standard for Arsenic The Safe Drinking Water Act, as amended

in 1996, requires EPA to revise the existing drinking water standard for arsenic.

EPA reduced the maximum level of arsenic allowed in drinking water that reduces the maximum level allowed from 50 parts per billion (ppb) to 10 ppb.

This has been challenged by the Bush Administration

New standard will be applied to all community water systems (serving 254 million people)

12% of these systems will likely have to take corrective action

Estimated National Cost:

3 ppb = 645 M$, 5 ppb = 379 M$10 ppb = 166 M$, 20 ppb = 65 M$

Fallonites, Don Cooper, 82, and wife Norma, 81, raise a toast to Nevada's arsenic-rich homebrew on the outskirts of town. Concentrations in drinking water are approximaately 100 ppb.

Outside magazine, February 2001

Data map: 31,350 ground-water arsenic samples collected in 1973-2001Data map: 31,350 ground-water arsenic samples collected in 1973-2001Ryker, S.J., Nov. 2001, Mapping arsenic in groundwater: Geotimes v.46 no.11, p.34-36.Ryker, S.J., Nov. 2001, Mapping arsenic in groundwater: Geotimes v.46 no.11, p.34-36.

ArsenicArsenicin Texas Groundwaterin Texas Groundwater

TWDB and NURE Data Sets

TWDB and NURE Data Sets

MolybdenumMolybdenumin Texas Groundwaterin Texas Groundwater

Geogenic Source of MetalsGeogenic Source of Metals

Catahoula formation, an oxidized Catahoula formation, an oxidized volcanic ash is a source of U, As, volcanic ash is a source of U, As, Mo and other trace metalsMo and other trace metals

Chromatographic SeparationChromatographic SeparationChromatographic SeparationChromatographic Separation

U MoSe As

Adopted from Devoto (1978)

OxidizedRegionally Reduced

South Texas Uranium Roll South Texas Uranium Roll FrontFront

Texas’ Uranium HistoryTexas’ Uranium History

““Oxidized” uranium ores were Oxidized” uranium ores were open-pit mined from sandstone-open-pit mined from sandstone-hosted roll-front deposits (1960 - hosted roll-front deposits (1960 - 1983)1983)

Open pit mining feasible because Open pit mining feasible because of shallow depth to ore (<300 feet) of shallow depth to ore (<300 feet) and the poorly cemented nature of and the poorly cemented nature of overburden overburden

Voluminous spoils stockpiled near Voluminous spoils stockpiled near pits. Two processing mills in pits. Two processing mills in western Karnes Co. generated large western Karnes Co. generated large tailings pilestailings piles

U Mining in the Nueces and U Mining in the Nueces and San Antonio River BasinSan Antonio River Basin

NuecesRiver

San AntonioRiver

Reduced sediments near the uranium ore were enriched in As, Mo, Se and radionuclides.Termed “protore” (proto ore), this material was placed on the top of spoil piles where it was most readily eroded.

Surface Exposure of ProtoreSurface Exposure of Protore

Oxidized overburden (upper strata) were placed at the bottom of spoilDeeper strata enriched in trace elements was placed on top of spoil.

Stratigraphic InversionStratigraphic Inversion

Eroded Spoil at the Haase Moy Eroded Spoil at the Haase Moy Wiatrek MineWiatrek Mine

Gonzales County

South Texas Ecological South Texas Ecological Impacts of MetalsImpacts of Metals

Molybdenosis in Black Angus Cattle, South Texas

Arsenic exposure to wildlife at ground water seeps in the Nueces River watershed

Arsenic in Texas Drinking WaterArsenic in Texas Drinking Water

What is the environmental legacy of What is the environmental legacy of U mining in South Texas…...U mining in South Texas…...

A littl’ TexasAdventure…A littl’ TexasAdventure…

Water Sample Collection

Water Sample Collection

Water Sample Water Sample ProcessingProcessing

Water Sample Water Sample ProcessingProcessing

Lyssy Lyssy PondPondLyssy Lyssy PondPond

Thermocline Stratified Water column Declining DO

0

50

100

150

200

250

300

350

400

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0

DO (mg/L) and pH

19.5 20 20.5 21 21.5

Temperature (C)

Dissolved Oxygen (mg/L) pH Temperature (C)

Redox cline

Arsenic Arsenic vs.vs. other oxyanions other oxyanionsLyssy Pond Profile - oxyanion ratios

0

50

100

150

200

250

300

350

400

0 20 40 60As/U

Depth (cm)

0 5 10 15

As/V

As/U

As/V

Station 1: DO Water Profile

0

2

4

6

8

10

12

14

0.0 2.0 4.0 6.0 8.0 10.0 12.0

Dissolved Oxygen (mg/L)

Depth (m)

July August January

O2 Boundary

O2 Boundary

Station 4: DO Water Profile

0

2

4

6

8

10

0.0 2.0 4.0 6.0 8.0 10.0 12.0

Dissolved Oxygen (mg/L)

Depth (m)

July August January

Virtually homogenous in Virtually homogenous in January and following the January and following the

episodic mixing event in Julyepisodic mixing event in July

Partial Partial stratification in stratification in

AugustAugust

Lake CCLake CC

DO ProfileDO Profile

August0

2

4

6

8

10

12

14

0 2 4 6 8 10 12 14 16

As (µg/L)

Depth (m)

Diss-Sta1Part-Sta1Diss-Sta4Part-Sta4

Oxic/Suboxic Interface

August0

2

4

6

8

10

12

14

0.0 0.5 1.0 1.5 2.0

U (µg/L)

Depth (m)

Diss-Sta1Part-Sta1Diss-Sta4Part-Sta4

Oxic/Suboxic Interface

The Distribution of As, Mo and UThe Distribution of As, Mo and U

Sta 10

2

4

6

8

10

12

14

0 2 4 6 8 10 12 14 16

As (µg/L)

Depth (m)

Aug

July

Jan

Temporal Distribution of AsTemporal Distribution of As

Arsenic levels elevated above ambient by an order of Arsenic levels elevated above ambient by an order of magnitude, depending on the hydrodynamic regime.magnitude, depending on the hydrodynamic regime.

Spatial Distribution of AsSpatial Distribution of As

0

2

4

6

8

10

12

Sta 1 Sta 2 Sta 4 Sta 5 Sta 6

Distribution of Arsenic in

Lake Corpus Christi

Jul-00 Aug-00 Jan-01

Background

0

5

10

15

20

25

30

35

40

45

50

ppb

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16Well Number

Arsenic

Uranium

Molybdenum

Ground WatersGround Waters

As As StdStd

U U Std.Std.

““Making prediction is very difficult, Making prediction is very difficult, especially about the future” – especially about the future” – Casey StengelCasey Stengel

Water scenarios: Projected and actual global withdrawals.Water scenarios: Projected and actual global withdrawals.From Gleick (2000): From Gleick (2000): The World’s Water, 2000-2001The World’s Water, 2000-2001

““Making predictions…”Making predictions…”

Water scenario: Regional management modelWater scenario: Regional management model

Aquiferrecharge

proposed

Pass through needsfor estuaries

Mary Rhodes pipeline

Geogenic source: conservative behavior Geogenic source: conservative behavior

As vs V

y = 1.063x + 2.0 r2 = 0.89

0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0

Dissolved As (µg/L)

Dissolvedl V (µg/L)

July

August

January

Tucson

CCTap

Geogenic source: conservative behavior Geogenic source: conservative behavior Arsenic Ratios in the Nueces River Watershed

0

20

40

60

80

100

0 2 4 6 8 10 12As/V

As/U

Lake Corpus Christi

Rivers

Groundwaters

Lyssy Pond

Uranium Mining

tap

Hydrodynamic control: evapoconcentration Hydrodynamic control: evapoconcentration

As Mass Balance - Lake CC

0.0

3.0

6.0

9.0

12.0

15.0

April MayJune JulyAugust

Sept Oct Nov Dec Jan FebMarchApril MayJune July

AugustMonth

As (ug/l)

0%

10%

20%

30%

40%

50%

60%

70%

CalculatedMeasured%Vol

M/M/t = Ct = CiiQQii – CQ – CQoo + R + Rdd – R – Rpp

AsAsLL((tt) = As) = AsLL((t-1t-1) + ([As]) + ([As]iiQQii) - ([As]Q) - ([As]Qoo))

[As]([As](tt) = As) = AsLL((tt)/Vol()/Vol(tt))

Implications of evapoconcentration Implications of evapoconcentration

1)1) Water management practices that take into Water management practices that take into consideration temporal changes (short-scale and consideration temporal changes (short-scale and short-lived)short-lived)

2)2) Management of water resources and overdrawn Management of water resources and overdrawn environments: Owens Lake and Salton Sea environments: Owens Lake and Salton Sea (California)(California)

Tucson’s Drinking WaterTucson’s Drinking Water

““Access to safe water is a Access to safe water is a fundamental human need and, fundamental human need and, therefore, a basic human right.therefore, a basic human right.

Contaminated water jeopardizes both Contaminated water jeopardizes both the physical and social health of all the physical and social health of all

people. It is an affront to human people. It is an affront to human dignity” dignity”

Kofi AnnanKofi Annan – – UN Secretary-General on UN Secretary-General on World Water DayWorld Water Day

Tucson’s drinking waterTucson’s drinking waterSelenium, Uranium, Arsenic, Vanadium Concentrations

in Tucson Drinking waters (ug/L)

0

2

4

6

8

10

12

NST ST STF BW

SeUAsV

Geochemical controls of As cycling:Geochemical controls of As cycling:– Fe/Mn oxyhydroxidesFe/Mn oxyhydroxides

As desorption at high pH under As desorption at high pH under oxidising conditionsoxidising conditions

As desorption and dissolution due to As desorption and dissolution due to changes in reducing conditionschanges in reducing conditions

Tucson’s water rechargeTucson’s water recharge

Tucson’s water recharge: TOCTucson’s water recharge: TOC

Tucson’s water recharge:Tucson’s water recharge:As in SweetwaterAs in Sweetwater

Outlook for As researchOutlook for As research

Hypothesis 1Hypothesis 1: The high alkalinity and pH of CAP waters will lead to : The high alkalinity and pH of CAP waters will lead to a rise of these properties in the Tucson recharged aquifer in turn a rise of these properties in the Tucson recharged aquifer in turn leading to desorption of As (and possibly other oxyanions) from the leading to desorption of As (and possibly other oxyanions) from the aquifer’s solid phase.aquifer’s solid phase.

Hypothesis 2Hypothesis 2: The incorporation of natural DOM from CAP waters : The incorporation of natural DOM from CAP waters into the aquifer will lead to decreased Ointo the aquifer will lead to decreased O22 concentrations and concentrations and changes in redox potential in these waters thus allowing for the changes in redox potential in these waters thus allowing for the dissolution of Fe/Mn hydroxides and subsequent desorption of dissolution of Fe/Mn hydroxides and subsequent desorption of oxyanions/anions.oxyanions/anions.

Hypothesis 3Hypothesis 3: Different areas of Tucson basin contain significantly : Different areas of Tucson basin contain significantly different concentrations of As and other oxyanions thus leading to different concentrations of As and other oxyanions thus leading to unequal exposure potential among specific populations.unequal exposure potential among specific populations.