Characteristics and use of an Characteristics and use of an aquifer recharged with untreated aquifer recharged with untreated wastewater (Emerging pollutant wastewater (Emerging pollutant

fate)fate)

Blanca JIMENEZBlanca JIMENEZ

Water Supply 85.7 m3/s

Mexico Valley Aquifer

60 m3/s of Sewage to irrigate 77,000 ha

Overexplotation =Overexplotation =Subsidence up to 40 cm/yr¡¡¡¡Subsidence up to 40 cm/yr¡¡¡¡

NEl Mezquital Valley(500,000 inhabitants)

Mexico City (21 million inhabitants)

66% Local groundwater18% Imported surface water 9% Reuse 6% Imported groundwater 1% Local surface water

Tula aquifer

100 km

25 m3/s infiltration

Groundwater uses:38% agriculture33 % industry17% drinking water 12% other uses

5.2 m3/s extraction

200m

Reuse of Mexico City’s wastewater

2% Industries + 6% Municipal + 5% Ecological

The rest, 87% is send and used to irrigate the Mezquital Valley (120 years)

BUTStill the is a deficit of 7 m3/s that will increase to 10 m3/s for 2010

Xochimilco “wetlands”Chapultepec recreative lakeVdM Power Plant

The Tula (Mezquital) Valley

Semi arid Climate (rainfall of 550 mm and

evaporation of 1 800 mm)

The soil is saline and with low content of

nitrogen, phosphorous and organic matter

In the 1930-40s the Government was thinking

on moving people

Mezquital ValleyMezquital Valley

With no WW With no WW With With

WWWW

Yield in Ton ha -1

Crop UntreatedWastewater

Natural water

% of increase

Maize 5 2 150

Barley 4 2 100

Tomato 35 18 94

Oats 22 12 83

Chili 12 7 71

Alfalfa 120 7 71

Wheat 3 2 50

Yield Increase due to WastewaterYield Increase due to Wastewater

Parasites Ages Morbidity rates

Raw wastewater

Natural water

Ratio

Ascaris lumbricoides(Helminth)

0 to 45 to 14

> 15

15.316.15.3

2.71.00.5

5.716.011.0

Giardia lamblia (Protozoa)

0 to 45 to 14

> 15

13.69.62.3

13.59.22.5

1.01.01.0

Entamoeba histolytica(Protozoa)

0 to 45 to 14

< 15

7.016.416.0

7.312.013.8

1.01.31.2

Gastrointestinal diseases

Wastewater Treatment Needs

To reduceTo reduce

HO < 1 ova/LHO < 1 ova/L

FC < 1000 MPN/100 mLFC < 1000 MPN/100 mL

but,but,

Preserving BOD, N, and PPreserving BOD, N, and P

Solution at 1/3 of the cost of the Solution at 1/3 of the cost of the conventional schemesconventional schemes

Water balance in the Mezquital Valley

60 m3/s Mexico City raw

wastewater

Since 1896

25 m3/s infiltration from irrigation

(13 fold natural recharge)

5.2 m3/s extraction

7.8 m3/s to other

valleys

38% agriculture

33 % industry

17% domestic consumption

12% other usesHigh Irrigation rate combined High Irrigation rate combined

with 688 km unlined channels with 688 km unlined channels

for wastewater distributionfor wastewater distribution

Tula Valley aquifer

<< year 1900 the groundwater level was at least at year 1900 the groundwater level was at least at

50 m below50 m below

Since 1997, artesian wells with flows from Since 1997, artesian wells with flows from 100 to 100 to

600 L/s600 L/s

Groundwater main source of drinking water of Groundwater main source of drinking water of

500,000500,000 inhabitants inhabitants

Reuse of Excess Volumes of Well La Noria in Swimming Poolsat Mezquital Valley, Mexico

Cerro Colorado Spring

Tezontepec SpringTezontepec Spring

Phase I(1995)

Rapid assessment of the quality of the water used as supply in the Mezquital Valley

Preliminary water qualityAssessment (4 laboratories in parallele)

GROUPANALYZED

PARAMETERS

Inorganic compoundsOrganic compoundsPhysicalMetalsNon-metalsMicrobiologicalOrganoleptic

9221

218683

Total 288

Parameter Sources not complying with drinking water standards

% Volume

TDS 95

Sodium 73

Fecal coliforms 25

Nitrates 12

Chlorides 10

Hardness 9

Sulfates 2

Fluorides 1

Without problem 5

Fecal Coliforms in wells on the WW irrigation fields not fulfilling construction requirements

EVALUATION OF DRINKING WATER SUPPLIES

44 parameters

ResultsResults No main problemsNo main problems

Water was light saline Water was light saline

In wells built with no care some In wells built with no care some microbiological problemmicrobiological problem

Why not using it for Mexico City Why not using it for Mexico City supply?supply?

Phase 2Phase 2

To determine the quality in a To determine the quality in a number of representative sites of number of representative sites of water supply systems for population water supply systems for population (175 000 inhab)(175 000 inhab)

PARAMETERS RESULT

Viruses ND

Helminth eggs ND

Acute toxicity (Microtox®)

ND

Pesticides ND

Atrazine < 0.5 ppb

Carbofuran < 0.5 ppb

2,4-D < 0.1 ppb

Other compounds “Chomatogram picks”

DRINKING WATER QUALITY IN El MEZQUITAL VALLEY

ND = NOT DETECTED

Location of sampling sites

Phase II BPhase II B

To determine the aquifer productivityTo determine the aquifer productivity

To determine the feasibility of extracting To determine the feasibility of extracting water for Mexico Citywater for Mexico City

ResultsResults

There are There are 33 different aquifers by its different aquifers by its quality and quantity/pathway of WW quality and quantity/pathway of WW rechargedrecharged

SDT is the main difference, and is due SDT is the main difference, and is due to WW infiltration pathwaysto WW infiltration pathways

Extraction up to 10 mExtraction up to 10 m33/s but /s but recommended to limit it to 6 mrecommended to limit it to 6 m33/s for a /s for a first phasefirst phase

Phase IIIPhase III(1997-99)(1997-99)

Identifying PICKS in chromatogramsIdentifying PICKS in chromatograms

With standardized methodsWith standardized methods

Having detection limits of µg/LHaving detection limits of µg/L

With out cleaning and derivitazing With out cleaning and derivitazing samplessamples

Selected compounds in wastewater Selected compounds in wastewater and groundwater in µg/Lgroundwater in µg/L

Compound Wastewatwe Site 1 Site 2 Site 3

Methyl (1-methy-ethyl)- benzene

5-10 < 5 < 5 < 5

1,1-oxy-bis-benzene 10-50 <5 < 5 < 5

4-nonyl phenol 1000 5-10 10-50 5-10

1,2,4 trichlorobenzene

5-10 <5 < 5 < 5

Benzenes 100 <5 < 5 < 5

Phenols 1500 10 50 10

PAH 25 <5 < 5 < 5

Importance of soil as treatment method to remove organic compound removal

PHASE IV Treatment processes to “reclaim” waterPHASE IV Treatment processes to “reclaim” water

WWTP Secondary effluent

Sand Filtration

OzonationActivated Carbon

filtration (1)

Membranes (NF+RO)Treated

effluent

Activated Carbon

filtration (2)

UV Disinfection

Chorine

Well water

Activated Carbon

Filtration Membranes (NF, RO)

UV Disinfection

Chlorine

Treated effluent

Treatment Processes for the secondary effluentTreatment Processes for the secondary effluent

4th Phase4th Phase

1 L/s pilot plant with membranes (OR and 1 L/s pilot plant with membranes (OR and NF)NF)

Membranes selected “conventionally”Membranes selected “conventionally”Molecular weightMolecular weightChemical composition (Al, Fe, Carbonates)Chemical composition (Al, Fe, Carbonates)

Application of membrane processes resultsRaw Wastewater

Well 115

Cerro Colorado Spring

Nanofiltration effluent

Springs water treatment Springs water treatment resultsresults

Filtration with Reverse Osmose or Filtration with Reverse Osmose or Nanofiltration are effectiveNanofiltration are effective

Chromatogram picks disappear, TDS less Chromatogram picks disappear, TDS less than 70 mg/L, but pH is acid with RO (Too than 70 mg/L, but pH is acid with RO (Too clean)clean)

NF with an APPROPRIATE membraneNF with an APPROPRIATE membrane

PHASE V

To identify and evaluate the flora and fauna living in the “Cerro Colorado Spring

to estimate the impact of toxics compounds

Cerro Colorado Spring

Origin It appeared 40 years ago as a natural exit of the Mezquital Valley aquifer due to the overload with raw wastewater

Diverse aquatic populations usually presented in Diverse aquatic populations usually presented in non polluted systemsnon polluted systems

1

10

100

1000

10000A

nelid

es

Hyale

llas

Sn

ail

s

Pla

tyh

elm

inth

es

Fre

sh

w

ate

r sh

rim

p

Macro

cyclo

ps

Ste

nto

r

Ostr

acod

a

Asellu

s

NU

MB

ER

SITE 1 SITE 2 SITE 3 SITE 4 SITE 5

Family Poecilidae

Genus Heterandria

Species H. jonesi

Family Goodeidae

Genus Allotoca

Species A. regal is

0

10

20

30

40

50

60

70

80

90

100

% o

f fis

h

Samples

Male 24 45 35 55

Female 76 55 65 45

1 2 3 4

Percentage of females and males in Percentage of females and males in fishesfishes

ARTHROPODS, ARTHROPODS, known as “Mexican known as “Mexican acocil”,acocil”, “indicators”of very clean water“indicators”of very clean water

SOURCESOURCE CapacityCapacity

mm33/s/sHeaHea

dd

mm

DistancDistancee

kmkm

Cost Cost

($/m($/m33))

TemascaltepeTemascaltepecc

5.05.0 15701570 8080 5.85.8

AmacuzacAmacuzac 13.513.5 17001700 100100 8.68.6

TecolutlaTecolutla 9.89.8 12661266 116116 8.58.5

Mezquital Mezquital ValleyValley

10 10 400400 7070 2.52.5

Mexico City Mexico City (Reuse)(Reuse)

>10>10 00 00 1515

Supply altenatives for Valley of Mexico

(2240 masl)

Years under WW irrigationYears under WW irrigation

1

UE Processes comparisonUE Processes comparison

1) 1) WW + SAT/SAR WW + SAT/SAR Potable water Potable water

2) 2) WW + MBR + Wetlands + SAT/SAR WW + MBR + Wetlands + SAT/SAR Potable water Potable water

3) 3) Tertiary + membranes + SAT/SAR Tertiary + membranes + SAT/SAR Potable waterPotable water

4) 4) Tertiary + SAT/SAR + Membranes Tertiary + SAT/SAR + Membranes Potable waterPotable water

5)……12)5)……12)

ResultsResults : Similar GW Composition : Similar GW Composition

Emerging Pollutants content in WW (Emisor Central)

Acid Compounds

• All detected but clofibric acid.

• Salicylic acid in content > than reported in literature (Ternes et al., 1998b).

• Naproxen >> content due to a > consumption

• Ibuprohene, 2,4-D, ketoprophene and gemfibrozyl, < content ( due to rapid photolysis)

Endocrine Disrupters compounds

•All detected

•Pentachlorophenol < content (photolysis)

Acid compound content in Tula Valley Water sources

Only 3 acid compounds (pharmaceutical) were detected.

Low content, presumably with not effects in humans, but in some cases in invertebrates and fish.

0

1

2

3

4

Man

zan

itas

No

. 1

Itu

rbe

S.

Fra

nci

sco

Bo

jay

El

Pu

ed

he

Cer

ro C

olo

rad

o

El

Ro

sari

o

El

Mex

e

Teo

fan

i

Cax

uxí

San

Sal

vad

or

Bo

thib

ají

No

.1

San

Is

idro

Po

zo G

ran

de

Co

nte

nt,

ng

/L

Ibuprophen Salicylic Acid Naproxen

TULA DE ALLENDE

2 compounds

ACTOPAN

2 Compounds

SAN SALVADOR

> 2 Compounds

FRANCISCO I. MADERO

0 Compounds

TEZONTEPEC

0 Compounds

Emerging Pollutant content in Water Sources

COMPOUND BLANK Cerro Colorado (ng/L)

El Puedhe Spring

El RosarioWell

SAMPLE 1 SAMPLE 2

Clofibric Acid nd nd nd

Ibuprofen <LOQ 2.2 (±1.2) 0.8 (±0.3) 0.54 0.92

Salicylic Acid 2.4 7.8 (±2.1) 9.6 (±12.2) 5.4 10.72

2,4-D <LOQ <LOQ <LOQ

Gemfibrozil <LOQ <LOQ <LOQ

Naproxen 0.40 0.8 (±0.2) 0.9 (±0.03) 0.94 0.41

Ketoprofen 0.31 <LOQ 0.1 (±0.04)

Diclofenac <LOQ <LOQ <LOQ 0.21 0.12

4-Nonylphenols 3.7 8 (±2) 1.8 (±2.3) 19.1 8.53

PCP <LOQ 0.20 (±0.07) 0.11 (±0.02)

Triclosan 0.13 1.3 (±0.2) 1.12 (±0.16) 0.17 0.12

bisphenol-A 0.20 0.4 (±0.17) 0.41 (±0.21) 0.39 0.52

BuBeP 0.60 2.0 (±1.2) 1.7 (±0.4)

DEHP 14.5 25 (±3) 6.6 (±3.6)

Estrone 0.005 0.17 (±0.02) 0.16 (±0.02)

17β-estradiol 0.002 0.02 (±0.003) 0.01 (±0.03)

EE2 <LOQ 0.06 (±0.02) <LOQ

Emerging pollutants in soils

• Two soil classes irrigated with raw wastewater for 90 years (Phaeozem and Leptosol)

• Surface layer (10 cm)

We found:• 3 pharmaceutical active

substances • 1 disinfectant • 2 industrial chemicals

0

1

2

3

4

5

6

7

carbamazepine naproxen ibuprofen

Conc

entr

ation

(ng

/g) Phaeozem

Leptosol

020406080

100120140

4-nonylphenols triclosan bisphenol A

Conc

entr

ation

(ng

/g) Phaeozem

Leptosol

Accumulation in soils

• Comparison between two ages under irrigation• Fine soil (Phaeozem)• Greater accumulation in soils with 10 years under irrigation• High biodegradation in soils with 90 years under irrigation

0

2

4

6

8

10

12

14

16

18

4.00 4.50 5.00 5.50 6.00

conc

entr

atio

n (n

g/g)

organic matter (%)

Triclosán (10 mg/L)Carbamazepine (17.7 mg/L)Naproxen sodium salt (266 mg/L)

We found:• A relationship between soil organic matter (SOM)

and retention of the compounds• Low solubility and high SOM = high retention in soil

Number in parentheses: Water solubility

0

0.1

0.2

0.3

0.4

0.5

0.6A

ccum

ulati

on g

/ha

yr

10 yrs 90 yrs

Migration through soil

• Fine soil (Phaeozem)• Displacement of 4-

nonylphenol towards the shallow aquifer

• High retention of Carbamazepine and possible degradation of anti-inflammatory drugs, triclosan and bisphenol A in soil surface layer.

0

20

40

60

80

100

120

0 3 5 8 10 13 15 18 20

dept

h (c

m)

concentration (ng/g)

ibuprofeno naproxeno carbamazepinaibuprof

ennaprox

encarbamaz

epine

0

20

40

60

80

100

120

0 25 50 75 100 125 150 175 200 225 250 275 300 325

dept

h (c

m)

concentration (ng/g)

triclosán bisfenol A 4-nonilfenoles4-

nonylphenols

4747

Conclusions

• Wastewater for irrigation is a source of pollutant for soil/water sources .•Contaminants content varies in wastewater, water sources and soil as well among sites •Ftalates are everywhere, event at the laboratory •Contaminants content is below limits (when available) . • Polar compounds are those to be found? •All the contaminants that have been looked for were found in Mexico City wastewater buy clofibric acid•Chemical drugs in higher content were salicilic acid and naproxene and concerning disrupting compounds , di-2 (etilhexil) ftalato y los 4-nonilfenoles.

J.C Durán-Álvarez; E. Becerril-Bravo; V. Silva; B. Jiménez; R. Gibson. The analysis of a group of acidic pharmaceuticals, carbamazepine, and potential endocrine disrupting compounds in wastewater irrigated soils by gas chromatography–mass spectrometry. Talanta. 2009, In press, doi:10.1016/j.talanta.2009.01.035.

Occurrence of pharmaceuticals active substances and potential endocrine disrupting compounds in wastewater irrigated soils from central México, UNESCO (in press).

Jiménez, B., Chávez A., Navarro I., Gibson R., Durán J.C., Guimarães A., Zarandayaa S. FATE OF EMERGING POLLUTANTS IN SOILS IRRIGATED WITH UNTREATED WASTEWATER– TULA VALLEY, MEXICO UNESCO-IHP Water Quality Case Study (in press)

  

Further workIndustrial Pretreatment programs Education and communication programsDevelopment of an appropriate regulation

AT A WORLD LEVEL, SEVERAL OTHER CASES HAVE BEEN REPORTED (WWT 20% LA, 5 % A and 25% ASIA)

+ PCP and ED in Developing countries surface water

Instituto de Ingeniería Instituto de Ingeniería UNAMUNAM

Three campus: Mexico City. Juriquilla Three campus: Mexico City. Juriquilla Queretaro and Cuernavaca MorelosQueretaro and Cuernavaca Morelos

In Mexico City all themes lead by PhD In Mexico City all themes lead by PhD full or assistant professorfull or assistant professor

Near 80 persons (Mexico City)Near 80 persons (Mexico City) Laboratories full equippedLaboratories full equipped Master ,PhD and postdoctoral Master ,PhD and postdoctoral

programs and scholarshipsprograms and scholarships