review of the use of atrazine and its occurrence and control in drinking … · 2016-01-22 ·...

Review of the Use of Atrazine Review of the Use of Atrazine and Its Occurrence and and Its Occurrence and

Control in Drinking WaterControl in Drinking Water

WATERWATERTECH 2008TECH 2008April 17, 2008April 17, 2008

Presented by:Presented by:Suzanne LazorkoSuzanne Lazorko--Connon, Connon, P.EngP.Eng..

OUTLINE OF PRESENTATIONOUTLINE OF PRESENTATIONWhat is atrazine?What is atrazine?

•• Uses, Chemical and Physical PropertiesUses, Chemical and Physical Properties•• Mode of Action, Mechanisms of DegradationMode of Action, Mechanisms of Degradation•• Environmental Fate and Transport Environmental Fate and Transport

Why atrazine? Why atrazine? Toxicology Toxicology

•• Animals, Humans, Aquatic LifeAnimals, Humans, Aquatic Life•• Acute, Chronic, CarcinogenicityAcute, Chronic, Carcinogenicity

Occurrence in WaterOccurrence in WaterCriteria Criteria

•• Freshwater Aquatic Life, Drinking WaterFreshwater Aquatic Life, Drinking WaterEfficiencies of Water Treatment Efficiencies of Water Treatment

•• GAC, PAC, OGAC, PAC, O33, AOP, AOP•• Membranes, Membranes, OrganoOrgano--ZeolitesZeolites

ConclusionsConclusions

WHAT IS ATRAZINE?WHAT IS ATRAZINE?

•• Synthetic organic herbicideSynthetic organic herbicide22--chlorochloro--44--ethylaminoethylamino--66--isopropylaminoisopropylamino--ss--triazinetriazine

•• Symmetric ChloroSymmetric Chloro--TriazineTriazine•• Developed in 1958Developed in 1958•• Registered in Canada in 1960Registered in Canada in 1960•• One of the Most Widely Used One of the Most Widely Used

Herbicides in the WorldHerbicides in the World

United States 2001 United States 2001 –– 2.3 billion kg 2.3 billion kg a.ia.i..Canada 1990 Canada 1990 –– 1.2 million kg 1.2 million kg a.ia.i..

2007 acreage corn planted 2007 acreage corn planted –– 1.4 million ha1.4 million ha93% of acreage in Ontario and Quebec93% of acreage in Ontario and Quebec

BroadBroad--leaf and grassy weed controlleaf and grassy weed controlCanada: CornCanada: CornOther Crops/Uses:Other Crops/Uses:

•• Sorghum, guava, sugar cane, citrus, pineapple, nut Sorghum, guava, sugar cane, citrus, pineapple, nut orchards, range grasses, pasture, conifer forests, Christmas orchards, range grasses, pasture, conifer forests, Christmas tree farms, tree farms, sodfarmssodfarms, summer fallow, golf courses, , summer fallow, golf courses, residential lawnsresidential lawns

USE OF ATRAZINEUSE OF ATRAZINE

Banned in European Union since 2004

Only province in Canada for which it is not registered for use: B.C. (since 2007)

USE OF ATRAZINEUSE OF ATRAZINE

2.33 2.33 –– 2.802.80Log KLog Kowow

2 2 -- 742 days742 daysField HalfField Half--lifelife

18,000 mg/L in methanol18,000 mg/L in methanolSolubility in Organic Solubility in Organic SolventSolvent

3 x 103 x 10--77 mm Hg at 20mm Hg at 20°°C C Vapour PressureVapour Pressure

3.4 x 103.4 x 10--99 atmatm--mm33/mol at 20/mol at 20°°C C HenryHenry’’s Law Constants Law Constant

39 39 –– 13,600mL/g13,600mL/gKKococ

28 28 –– 33 mg/L at 2033 mg/L at 20°°C; C; 70 mg/L at 2570 mg/L at 25°°CC

Solubility in WaterSolubility in Water1.87 g/cm3 at 201.87 g/cm3 at 20°°CCDensityDensity175 175 –– 177177°°CCMelting PointMelting Point

CHEMICAL & PHYSICAL PROPERTIESCHEMICAL & PHYSICAL PROPERTIES

(Adapted from (Adapted from CalEPACalEPA, 1999; Liu, 1999), 1999; Liu, 1999)

MODE OF ACTIONMODE OF ACTION

Susceptible PlantsSusceptible Plants ⇒⇒ Inhibits the Hill Inhibits the Hill reaction of photosynthesisreaction of photosynthesis

Tolerant PlantsTolerant Plants ⇒⇒ MetabolizedMetabolized

MECHANISMS OF DEGRADATIONMECHANISMS OF DEGRADATION

Primary chemical (Primary chemical (abioticabiotic) ) degradationdegradation ⇒ ⇒ hydrolysis to hydrolysis to hydroxyatrazinehydroxyatrazine

Primary microbial degradationPrimary microbial degradation ⇒ ⇒ NN--dealkylationdealkylation of the side chains to of the side chains to chlorinated metabolites: chlorinated metabolites: deethylatrazinedeethylatrazine & & deisopropylatrazinedeisopropylatrazine

ENVIRONMENTAL FATE AND ENVIRONMENTAL FATE AND TRANSPORTTRANSPORT

GroundwaterGroundwaterPersists for long periods of time in aquifersPersists for long periods of time in aquifersUSEPA USEPA –– 11% of wells > 3 11% of wells > 3 μμg/Lg/L

Surface WaterSurface Waterhalfhalf--life in Lake Michigan water column est. life in Lake Michigan water column est. 13.9 years13.9 years

WHY ATRAZINE?WHY ATRAZINE?

Identified as a possible Endocrine Identified as a possible Endocrine Disrupting Compound by Environment Disrupting Compound by Environment CanadaCanada

Is ubiquitous in surface and Is ubiquitous in surface and groundwatersgroundwaters

Has been Has been labelledlabelled as the new DDT as the new DDT ––malformations observed in amphibiansmalformations observed in amphibians

WHY ATRAZINE?WHY ATRAZINE?USEPA USEPA -- Priority A chemical for potential Priority A chemical for potential groundwater contaminationgroundwater contamination

Agriculture Canada Agriculture Canada -- Ranked highest of 83 Ranked highest of 83 pesticides for potential of groundwater pesticides for potential of groundwater contaminationcontamination

European Commission European Commission -- Is one of the 33 Is one of the 33 priority substances of major concern in priority substances of major concern in European waters to be monitored under European waters to be monitored under the Water Framework Directive the Water Framework Directive

DogsDogs

Chronic Effects Chronic Effects included:included:

CardiopathyCardiopathy

SpragueSprague––DawleyDawleyRatsRats

Acute Effects: Acute Effects: inhibited the estrogeninhibited the estrogen--induced surge of theinduced surge of theluteinizingluteinizing hormonehormonebrain is the primary target site for effect of brain is the primary target site for effect of atrazine on control of ovarian functionatrazine on control of ovarian function

Carcinogenicity:Carcinogenicity:mammary mammary fibroadenomasfibroadenomas and and adenocarcinomasadenocarcinomas increasedincreased

ANIMAL TOXICOLOGYANIMAL TOXICOLOGY

HUMAN TOXICOLOGYHUMAN TOXICOLOGY

few studies conductedfew studies conducted

not likely to be carcinogenic in humansnot likely to be carcinogenic in humans

endocrine perturbations in rats may beendocrine perturbations in rats may berelevant to humansrelevant to humans

Intrauterine Growth Retardation studyIntrauterine Growth Retardation study

Concerns for the effect of the Concerns for the effect of the neuroendocrine mode of action on theneuroendocrine mode of action on thedevelopment of the young remaindevelopment of the young remain

Frogs Frogs

African ClawedAfrican Clawed Green frogGreen frog

Chronic EffectsChronic Effects

delay of metamorphosis

hermaphroditism is controversial

Chronic EffectsChronic Effects

survival decreased at lower concentrations

AQUATIC TOXICOLOGYAQUATIC TOXICOLOGY

Grass carpsalmon

Rainbow trout

Apoptosis (cell death) in carp cells

FishFish

Affects neurophysiological responses; affects behavioral responses based on olfaction

Reduction in the pheromonal-mediated endocrine function

Acute ToxicityAcute Toxicity

Freshwater Bivalve

bioaccumulation more efficient at low concentrations (~80 μg/L)

ShellfishShellfishAQUATIC TOXICOLOGYAQUATIC TOXICOLOGY

OCCURRENCE IN WATEROCCURRENCE IN WATERMost common contaminant in surface and Most common contaminant in surface and groundwaters (>70% detections in water on groundwaters (>70% detections in water on agricultural lands, urban areas and major agricultural lands, urban areas and major rivers and aquifers with mixed land use rivers and aquifers with mixed land use (1999))(1999))

Ontario 0.005 to 14.9 Ontario 0.005 to 14.9 μμg/L (2004)g/L (2004)

Quebec (4 river study) 98.7% detection (2004)Quebec (4 river study) 98.7% detection (2004)

up to 200 up to 200 μμg/L in streams of the g/L in streams of the MidMid--Western United States (1998)Western United States (1998)

21 21 μμg/L in groundwater (1982g/L in groundwater (1982--95 study)95 study)

FRESHWATER AQUATIC LIFE CRITERIAFRESHWATER AQUATIC LIFE CRITERIA

Canada: 1.8 Canada: 1.8 μμg/Lg/L

USEPA (2001 draft): Acute USEPA (2001 draft): Acute –– 350 350 μμg/Lg/LChronic Chronic –– 12 12 μμg/Lg/L

N/A[Analytical limit of

determination]

20040.1*(Guideline)

Australia

N/A[Treatment

Achievability]

19980.1*(Standard)

European Union

Mammary tumours (adenocarcinoma and

fibroadenoma) observed in female rats

19990.15(Health Goal)

California EPA PHG

N/A[Greater health

protection, technical feasibility and costs]

20031(Standard)

California EPA

Mammary tumours in female rats;

adenocarcinomas and carcinosarcomas in

male rats

19932(Guideline)

World Health Organization

Increased heart and liver weights in female

beagle dogs

19913(Health Advisory)

USEPA

Reduced body weight in offspring of 2nd

generation rats

19935* (Interim Guideline)

Health Canada

TOXICOLOGICAL ENDPOINT

YearCRITERIA (μg/L)AGENCY

* - includes metabolitesN/A – No toxicological endpoint used

DRINKING WATER CRITERIADRINKING WATER CRITERIA

OCCURRENCE IN DRINKING OCCURRENCE IN DRINKING WATERWATER

Occurrence of Atrazine in Finished Water in the U.S. Corn Belt oOccurrence of Atrazine in Finished Water in the U.S. Corn Belt of the Midf the Mid--West: 2002West: 2002--0404CRITERIA = 3 CRITERIA = 3 μμg/Lg/L

1.13.97Texas

2.114.63Ohio

1.25.91Missouri

2.311.38Louisiana

1.98.42Kentucky

2.6612.76Kansas

0.733.14Iowa

3.2230.48Indiana

1.8339.69Illinois

Mean concentration μg/LMax. Concentration (μg/L)State

[adapted from USEPA, 2006][adapted from USEPA, 2006]

OCCURRENCE IN DRINKING OCCURRENCE IN DRINKING WATERWATER

Occurrence of Atrazine in Finished Water in Ontario and QuebecOccurrence of Atrazine in Finished Water in Ontario and Quebec`̀CRITERIA = 5 CRITERIA = 5 μμg/Lg/L

0.070.9Quebec* (2001-2005)

0.159.9Ontario (1995-2005)

Mean concentration μg/LMax. Concentration (μg/L)Province

**-- including metabolitesincluding metabolites

[adapted from MOE, 2006; MDDEP, 2008][adapted from MOE, 2006; MDDEP, 2008]

REMOVAL OF ATRAZINE FROM REMOVAL OF ATRAZINE FROM WATERWATER

Conventional Treatment Technologies Conventional Treatment Technologies -- notnoteffectiveeffective

RecommendedRecommended Best Available TechnologyBest Available Technology(BAT) is GAC (BAT) is GAC

GACGACPACPACOO33 and AOPand AOPMembranesMembranesOrganoOrgano--ZeolitesZeolites


GACGACChemically Activated Fibers (Chemically Activated Fibers (CAFsCAFs) ) •• greatly improved adsorption effectivenessgreatly improved adsorption effectiveness•• 2 x number of bed volumes prior to2 x number of bed volumes prior to

breakthrough in presence of breakthrough in presence of humichumic acidacid•• regeneration possibleregeneration possible

NOM interference NOM interference


REMOVAL OF ATRAZINE REMOVAL OF ATRAZINE FROM WATERFROM WATER

[After [After YueYue et al., 2006]et al., 2006]

PACPACIncreased dosages required than isIncreased dosages required than is

typically used typically used •• 20 to 50 mg/L 20 to 50 mg/L –– 90% removal90% removal•• can partially remove atrazinecan partially remove atrazine•• dependent upon process conditions and sourcedependent upon process conditions and source

water characteristicswater characteristics•• NOM interferenceNOM interference



[After [After JiangJiang et al., 2006]et al., 2006]

OO3 3 and AOP (Oand AOP (O33/H/H22OO22))difficult to oxidize difficult to oxidize

trace levels still present (Otrace levels still present (O33))

formation of formation of bromatebromate (a possible(a possiblecarcinogen) in high bromide waterscarcinogen) in high bromide waters


[After [After AceroAcero et al., 2000]et al., 2000]


With only OWith only O33

With OWith O33 and Hand H22OO22


OO3 3 and AOP and AOP concon’’ddTiOTiO22 plus Splus S22OO88

--22 –– mineralized to mineralized to cyanuric acidcyanuric acid

[after Perez et al., 2006]

NanofiltrationNanofiltrationretention appears dependent on the retention appears dependent on the presence of NOM; 36% removalpresence of NOM; 36% removal

independent of the initial concentration ofindependent of the initial concentration ofatrazineatrazine

double membrane required to achievedouble membrane required to achieveEUEU’’ss standardstandard


[after Devitt et al., 1998]


OrganoOrgano--ZeolitesZeolitesmodified modified organoorgano--zeolitezeolitemonolayer monolayer –– maximum adsorption maximum adsorption achievedachievedsorption of atrazine decreased with sorption of atrazine decreased with increasing adsorbent particle sizeincreasing adsorbent particle sizeadsorbent in suspension: increase adsorbent in suspension: increase adsorption with increased adsorbent adsorption with increased adsorbent concentrationconcentration



[after Lemic et al., 2006]

CONCLUSIONSCONCLUSIONSAtrazine is ubiquitous in surface and Atrazine is ubiquitous in surface and groundwatergroundwaterEndocrine disrupting effects:Endocrine disrupting effects:

•• earlier onset of menopause in ratsearlier onset of menopause in rats•• may be relevant to human reproductive may be relevant to human reproductive

developmentdevelopment•• noted at very low concentrations innoted at very low concentrations in

amphibians (frogs)amphibians (frogs)

Criteria for drinking water varies significantly Criteria for drinking water varies significantly across agenciesacross agenciesConventional treatment technologies not Conventional treatment technologies not effective at removaleffective at removalTertiary treatment appear to not achieveTertiary treatment appear to not achievesignificant removals; NOM and source significant removals; NOM and source water present challenges for its removalwater present challenges for its removal

QUESTIONS?QUESTIONS?

review of the use of atrazine and its occurrence and control in drinking … · 2016-01-22 ·...

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