Historic Oilfield Arsenic Sources: Historic Oilfield Arsenic Sources: Implications for a Pit Groundwater Implications for a Pit Groundwater

Model, Lake St. John Field, LA,Model, Lake St. John Field, LA,An UpdateAn Update

Mary L. Barrett, Ph.D.Mary L. Barrett, Ph.D.Consulting Geologist & Oilfield HistorianConsulting Geologist & Oilfield Historian

Shreveport, LAShreveport, LAmbarrett@centenary.edumbarrett@centenary.edu

2222ndnd International Petroleum Environmental ConferenceInternational Petroleum Environmental ConferenceNovember 17November 17--19, 201519, 2015------Denver, CODenver, CO

Presentation ObjectivesPresentation ObjectivesLake St. John Field, Concordia Parish, LALake St. John Field, Concordia Parish, LA

Update my IPEC 2014 talk to consider multiple hypotheses for origin Update my IPEC 2014 talk to consider multiple hypotheses for origin of elevated shallow groundwater (GW) arsenic (As), iron (Fe) and of elevated shallow groundwater (GW) arsenic (As), iron (Fe) and chlorides (chlorides (ClCl) below old oilfield pits) below old oilfield pitsHistorically arsenic (as corrosion inhibitor & possible herbicide) was Historically arsenic (as corrosion inhibitor & possible herbicide) was used in the field; this arsenic origin in considered in evaluating used in the field; this arsenic origin in considered in evaluating origins(s) of shallow origins(s) of shallow groundwater elevated arsenic in tank battery and groundwater elevated arsenic in tank battery and origins(s) of shallow origins(s) of shallow groundwater elevated arsenic in tank battery and groundwater elevated arsenic in tank battery and emergency pit areas emergency pit areas Consider if data (as of 4/15) reasonably support a 2008 reductiveConsider if data (as of 4/15) reasonably support a 2008 reductive--dissolution GW pit model to partially or completely explain elevated dissolution GW pit model to partially or completely explain elevated arsenic patterns arsenic patterns Point out several interesting questions arising from unique data Point out several interesting questions arising from unique data set, including: if/how sedimentset, including: if/how sediment--water equilibrium reflected; regional water equilibrium reflected; regional controls over ORP; importance of added iron/HFOs to arsenic (As) controls over ORP; importance of added iron/HFOs to arsenic (As) patterns; arsenic (As) geochemical associations above or at patterns; arsenic (As) geochemical associations above or at background levels and variations; significance of pitbackground levels and variations; significance of pit--area area groundwater data taken within first year of pit closures groundwater data taken within first year of pit closures

Public Record Usage for InterpretationsPublic Record Usage for Interpretations

The example from LSJ Field, LA, has a large public record The example from LSJ Field, LA, has a large public record available due to litigation (court records in one case) and available due to litigation (court records in one case) and especially due to LA Act 312 (2006+) & LA Office of especially due to LA Act 312 (2006+) & LA Office of Conservation (OOC) oversight of oilfield cleanup of oilfield Conservation (OOC) oversight of oilfield cleanup of oilfield litigation “legacy” sites (reports, raw data; hearing litigation “legacy” sites (reports, raw data; hearing records…)records…)records…)records…)I was a defense expert retained in the two cases that I was a defense expert retained in the two cases that generated public records above; geologist, oilfield generated public records above; geologist, oilfield historian (environmental companies responsible for historian (environmental companies responsible for analytical data: ICON; Pisani & Assoc., some Geosyntec)analytical data: ICON; Pisani & Assoc., some Geosyntec)Work on the last case ended Feb. 2014; I have pursued Work on the last case ended Feb. 2014; I have pursued this research since then, not retained concerning it, no this research since then, not retained concerning it, no discussions with past litigation experts (my opinions)discussions with past litigation experts (my opinions)

Study Area Study Area

(Modified from Pisani & Associates report, 2008;LA OOC file # 006-007)

Lake St. John Field ExampleLake St. John Field Example

Discovered in 1942, Tensas & Concordia Discovered in 1942, Tensas & Concordia Parishes, LAParishes, LAMajor producing field for The California Major producing field for The California Company (Standard Oil of CA, later Chevron)Company (Standard Oil of CA, later Chevron)Company (Standard Oil of CA, later Chevron)Company (Standard Oil of CA, later Chevron)Both unit (Cretaceous & some Tertiary age) & Both unit (Cretaceous & some Tertiary age) & lease productionlease production (Wilcox Fm mainly)(Wilcox Fm mainly)Outline of field study interpretationsOutline of field study interpretations–– Public records indicate 1950s arsenic corrosion inhibitor usagePublic records indicate 1950s arsenic corrosion inhibitor usage–– Shallow groundwater geochemistry around old emergency pit Shallow groundwater geochemistry around old emergency pit

areas documents its impactareas documents its impact

LA groundwater published arsenic record limited, but Miss. R. alluvium waters can be elevated (USGS 2000)

Groundwater Arsenic

be elevated (USGS 2000)

Modern work, shallow groundwater As valuesfrom S. LA, 78 wells,up to 0.200 mg/l(Yang et al, 2014)

Basic Model: Reductive Dissolution of Iron OxidesBasic Model: Reductive Dissolution of Iron Oxides

Fe oxides common in our Fe oxides common in our LA LA sediment, possible As sediment, possible As absorbedabsorbedAs released into GW with As released into GW with “reductive dissolution” “reductive dissolution” when some cause for a when some cause for a reducing environment reducing environment (organics, oil, clay…)(organics, oil, clay…)(organics, oil, clay…)(organics, oil, clay…)Fe oxides reFe oxides re--precipitate as precipitate as GW move into oxidizing GW move into oxidizing zone, rezone, re--absorb Asabsorb AsModel looks for relations Model looks for relations between ORP, Fe, Asbetween ORP, Fe, AsDoes not address Does not address anthopogenicanthopogenic As, FeAs, FeDoes not address As Does not address As desorption (phosphates)desorption (phosphates)

(Diagram modified from petroleum refinery & oil spillexample, Ghosh et al., 2003)

Groundwater Arsenic Geochemical Groundwater Arsenic Geochemical Models & Oil Field SitesModels & Oil Field Sites

Arsenic models are useful, Arsenic models are useful, butbut–– model study areas extrapolated model study areas extrapolated to Gulf Coast oilfield to Gulf Coast oilfield

regions of different geology & hydrogeology, regions of different geology & hydrogeology, andand–– a model may not consider impacts from “oilfield a model may not consider impacts from “oilfield

chemistry” and anthropogenic activitieschemistry” and anthropogenic activitieschemistry” and anthropogenic activitieschemistry” and anthropogenic activities

Waste “oilfield chemistry” has a history, & pits Waste “oilfield chemistry” has a history, & pits often record this historyoften record this historyModels need to consider Models need to consider anthropogenic anthropogenic possibilities possibilities in these old oil fields and other in these old oil fields and other industrial sitesindustrial sites

Amorphous Iron Precipitates: Long History of Study in Amorphous Iron Precipitates: Long History of Study in Oilfield Chemistry (Hydrous ferric oxidesOilfield Chemistry (Hydrous ferric oxides——HFOs)HFOs)

1950s Oilfield Water Treatment (Powell & Johnson, 1 952)

Iron Analyses, LSJ Field Produced WaterIron Analyses, LSJ Field Produced Water

1945 analysis, 14 ppm (Cl 13,820 ppm)1945 analysis, 14 ppm (Cl 13,820 ppm)1959 analysis, 90 ppm (Cl 80,908 ppm)1959 analysis, 90 ppm (Cl 80,908 ppm)1970 analysis, 215 ppm (Cl 101,135 ppm)1970 analysis, 215 ppm (Cl 101,135 ppm)1995 analysis, 21 mg/l (Cl 59,449 ppm)1995 analysis, 21 mg/l (Cl 59,449 ppm)1995 analysis, 21 mg/l (Cl 59,449 ppm)1995 analysis, 21 mg/l (Cl 59,449 ppm)

GENERAL OBSERVATION: Many oil fields had decades ( into 1970s, esp.) of elevated dissolved iron in produced water, and thus potentially into pits

(LA OOC, Tensas Poppadoc hearing files, 2009;

Norman reliance documents, v. 52-53)

Historic Arsenic Uses/Contaminants w/ Historic Arsenic Uses/Contaminants w/ Potential Environmental SignaturesPotential Environmental Signatures

Pesticides Pesticides –– Concordia Parish cotton, 1910+Concordia Parish cotton, 1910+–– Vegetable gardens, treesVegetable gardens, trees–– Cattle dipping vatsCattle dipping vats

HerbicidesHerbicides–– Inorganic & organicInorganic & organic–– Land & aquatic weed killerLand & aquatic weed killer

Oilfield usage documentedOilfield usage documented

IndustrialIndustrial–– Corrosion inhibitorCorrosion inhibitor–– Oilfield waste (produced Oilfield waste (produced

water, barite mud sulfide water, barite mud sulfide impurities, oil,…)impurities, oil,…)

–– Detergents, fertilizers Detergents, fertilizers (phosphorous)(phosphorous)

–– OtherOther

Griffin presentation onoilfield legacy litigation (2006)

Anthropogenic Arsenic in OilfieldsAnthropogenic Arsenic in OilfieldsContinued (cow studies)Continued (cow studies)

Veterinary journals document the presence of Veterinary journals document the presence of anthropogenic arsenic used around oilfield anthropogenic arsenic used around oilfield facilities facilities Recognized around pits, tanks and flowlinesRecognized around pits, tanks and flowlinesRecognized around pits, tanks and flowlinesRecognized around pits, tanks and flowlinesPast usages in oil fields Past usages in oil fields –– as “rust inhibitor and herbicide” (Coppock & as “rust inhibitor and herbicide” (Coppock &

others, 1996)others, 1996)–– as “soil sterilant” (“Nas “soil sterilant” (“N--solsol--40” w/ 400,000 ppm arsenic; 40” w/ 400,000 ppm arsenic;

Morgan & others, 1984)Morgan & others, 1984)–– As “corrosion inhibitor” (Edwards & others, 1979)As “corrosion inhibitor” (Edwards & others, 1979)

OilField Arsenic Corrosion InhibitorsOilField Arsenic Corrosion InhibitorsHistoric U. S. SummaryHistoric U. S. Summary

Acid Corrosion InhibitorAcid Corrosion Inhibitor–– 19321932, Michigan oilfield acid , Michigan oilfield acid

job, limestonejob, limestone–– 19341934, arsenic is important acid , arsenic is important acid

job inhibitor, but organics now job inhibitor, but organics now availableavailable

–– Early 1960sEarly 1960s, decrease As , decrease As

Production Corrosion InhibitorProduction Corrosion Inhibitor–– 19491949, Reported first usage in , Reported first usage in

Texas Wilcox trend Texas Wilcox trend (Jones, 1955)(Jones, 1955)

–– 19541954, CA survey, 17 fields;, CA survey, 17 fields;65 % pumping wells used 65 % pumping wells used inorganic inhibitors (arsenical inorganic inhibitors (arsenical –– Early 1960sEarly 1960s, decrease As , decrease As

usage, but good for highusage, but good for high--T T wellswells

–– In 1970sIn 1970s, arsenic inhibitor , arsenic inhibitor phasephase--out in acid jobsout in acid jobs

inorganic inhibitors (arsenical inorganic inhibitors (arsenical compounds and chromates) compounds and chromates) (Hill & Davie, API, 1955)(Hill & Davie, API, 1955)

–– 19571957, LA Stream Control , LA Stream Control Commission minutes report Commission minutes report phasephase--out of oilfield arsenic out of oilfield arsenic corrosion pellets, stripper corrosion pellets, stripper fields fields

–– 19601960, general end of U. S. , general end of U. S. oilfield arsenic corrosion oilfield arsenic corrosion inhibitors (Gardner, 1963); inhibitors (Gardner, 1963); move to organicsmove to organics

Iron & 1950s Arsenic Inhibitor in Produced Iron & 1950s Arsenic Inhibitor in Produced Water (Wilcox Trend, Texas)Water (Wilcox Trend, Texas)

Jones (1955) (Jones, 1955)

LSJ Field Public Documents, Arsenic LSJ Field Public Documents, Arsenic Corrosion InhibitorsCorrosion Inhibitors

(LA OOC Tensas Poppadoc hearing, 2009; Miller/ICON reliance documents, v. 28;Tensas/Miller 02469-02470)

WW--41 History41 History

WW--41, an arsenic corrosion inhibitor patented by 41, an arsenic corrosion inhibitor patented by Standard Oil of CA, is one example of arsenic Standard Oil of CA, is one example of arsenic corrosion inhibitors used in some 1950s oilfields of corrosion inhibitors used in some 1950s oilfields of the U.S.the U.S.

Its history is available in public documents.Its history is available in public documents.

WW--41 History41 History

California Research California Research Corp Corp (As & oilfield corrosion)(As & oilfield corrosion)–– Dec 1950, 2 Dec 1950, 2

patents, Rohrback et al patents, Rohrback et al (1954)(1954)

–– Mar 1951, 2 patents,Mar 1951, 2 patents,

California SprayCalifornia Spray--Chemical CorpChemical Corp

–– Mar 1951, 2 patents,Mar 1951, 2 patents,Rohrback et al (1953)Rohrback et al (1953)

–– Dec 1951, patent,Dec 1951, patent,Rohrback et al (1953)Rohrback et al (1953)

–– Oct 1954, patent, Oct 1954, patent, Frisius (1959)Frisius (1959)

–– 1952, trademark 1952, trademark application granted for application granted for “Ortho W“Ortho W--41,” also used is 41,” also used is “W“W--41,” for arsenic 41,” for arsenic corrosion inhibitor (42 % corrosion inhibitor (42 % sodium arsenite) sodium arsenite) (EPA, 1973)(EPA, 1973)

(My Opinion from the public record: W -41 was used in the LSJ Field in the 1950s; organic inhibitors were used after th at)

LSJ Field Study Area: Lease Tank Battery LSJ Field Study Area: Lease Tank Battery and SWD Emergency Pitsand SWD Emergency Pits

Mississippi River Mississippi River Alluvium & Aquifer at Alluvium & Aquifer at

LSJ FieldLSJ Field

–– Braided stream gravels at Braided stream gravels at base; cuts into underlying base; cuts into underlying base; cuts into underlying base; cuts into underlying Catahoula Fm sandsCatahoula Fm sands

–– Mostly pointMostly point--bar sandsbar sands–– FiningFining--up into up into

levee, overbank, floodplailevee, overbank, floodplain deposits (clay/silt)n deposits (clay/silt)

–– This nearThis near--surface unit is surface unit is aquifer’s confining layeraquifer’s confining layer

(Typical near-surface section from Pisani & Assoc., 2008; LA OOC file # 006-007)

1968 Pit Descriptions, Study Area1968 Pit Descriptions, Study Area

Applegate Pit Applegate Pit (closed ~ 1984; re(closed ~ 1984; re--closed 2007)closed 2007)–– 70’ x 150’ x 8’ (include 2’ levee)70’ x 150’ x 8’ (include 2’ levee)–– Usage “only in emergency”Usage “only in emergency”

Wilcox Pit Wilcox Pit (closed 1990)(closed 1990)–– 100’ x 100’ x 8’ (include 2’ levee)100’ x 100’ x 8’ (include 2’ levee)–– Usage “well backwashing” (and emergency)Usage “well backwashing” (and emergency)

Pan American Pit Pan American Pit (closed ~ 1984; re(closed ~ 1984; re--closed closed 2010)2010)–– 150’ x 200’ x 8’ (include 2’ levee)150’ x 200’ x 8’ (include 2’ levee)–– Usage “only in emergency”Usage “only in emergency”

(LA OOC Tensas-Poppadoc hearing; exhibit Tensas/Miller 2455-56)

FineFine--grained Unit Thicknessgrained Unit Thickness

(data from all soil boring descriptions of ICON, Pisani & Assoc., andGeosyntec; meander & swale lines after Saucier, 1967)

Shallow Groundwater Data (8’ to 22’ Shallow Groundwater Data (8’ to 22’ below surface) Used in This Talkbelow surface) Used in This Talk

The analyses from Pisani & Associates, ICON The analyses from Pisani & Associates, ICON (G. Miller), are numerous and of high(G. Miller), are numerous and of high--quality quality (Geosyntec data are limited but of high(Geosyntec data are limited but of high--quality)quality)Shallow groundwater data are most reflective of Shallow groundwater data are most reflective of potential old oilfield impacts & possible potential old oilfield impacts & possible potential old oilfield impacts & possible potential old oilfield impacts & possible controlling influences in pit areascontrolling influences in pit areasGroundwater wells at deeper depths (60’Groundwater wells at deeper depths (60’--80’, + 80’, + below surface) do not have arsenic values below surface) do not have arsenic values above natural variability range; deeper alluvium above natural variability range; deeper alluvium waters are a variation within the larger waters are a variation within the larger sediment/water geochemical systemsediment/water geochemical system

What is the LSJ Field Area’s Dissolved What is the LSJ Field Area’s Dissolved Arsenic Natural Variability?Arsenic Natural Variability?

Pisani & Associates (2012 report; LA OOC file Pisani & Associates (2012 report; LA OOC file # 007# 007--007) interpret the natural range from non007) interpret the natural range from non--detect detect (ND) up to 0.12 mg/l(ND) up to 0.12 mg/lA study in shallow allluvium across the River in Mississippi A study in shallow allluvium across the River in Mississippi has an As range of ND to 0.10 mg/l (Welsh et al, 2010; has an As range of ND to 0.10 mg/l (Welsh et al, 2010; has an As range of ND to 0.10 mg/l (Welsh et al, 2010; has an As range of ND to 0.10 mg/l (Welsh et al, 2010; also phosphorous)also phosphorous)ICON data from Tensas Parish landfill, ND up to 0.16 mg/l ICON data from Tensas Parish landfill, ND up to 0.16 mg/l (~ 25 mi away, 1994 to 2014 data, LDEQ EDMS # AI (~ 25 mi away, 1994 to 2014 data, LDEQ EDMS # AI 43506)43506)The LSJ field study area has localized shallow The LSJ field study area has localized shallow groundwater measurements above these values groundwater measurements above these values Limited arsenic species measurements at LSJ field; both Limited arsenic species measurements at LSJ field; both arsenic species were present (As III and As V) in similar arsenic species were present (As III and As V) in similar amountsamounts

Arsenic in Pit Soils, Sediment, & WatersArsenic in Pit Soils, Sediment, & Waters

55 years after alleged As usage, the pit solids of today 55 years after alleged As usage, the pit solids of today have arsenic ranges within Parish soil ranges have arsenic ranges within Parish soil ranges –– Pits modified, rebuilt 2Pits modified, rebuilt 2--3 times during usage3 times during usage–– Pan Am & Applegate pit closure ~1984; both rePan Am & Applegate pit closure ~1984; both re--closed closed

(Applegate 2007; Pan Am 2010); Wilcox pit closed in 1990(Applegate 2007; Pan Am 2010); Wilcox pit closed in 1990–– As analyzed in soils/sediment range from 1 to 10 mg/kg; one As analyzed in soils/sediment range from 1 to 10 mg/kg; one

(Deuel,1987) Wilcox pit sample at 16.9 mg/kg(Deuel,1987) Wilcox pit sample at 16.9 mg/kg(Deuel,1987) Wilcox pit sample at 16.9 mg/kg(Deuel,1987) Wilcox pit sample at 16.9 mg/kg

A 1984 G & E study found dissolved arsenic in brackish A 1984 G & E study found dissolved arsenic in brackish waters within the Applegate (0.04 mg/l) and Pan Am waters within the Applegate (0.04 mg/l) and Pan Am (0.05 mg/l) pits. The 2 ft of bottom sludge ranged from 3 (0.05 mg/l) pits. The 2 ft of bottom sludge ranged from 3 to 4.5 mg/kg Asto 4.5 mg/kg As

(LA OOC Tensas Poppadoc hearing, exhibits Tensas/Miller (LA OOC Tensas Poppadoc hearing, exhibits Tensas/Miller 0015200152--0051000510;;LA OOC file # LA OOC file # 006006--007007, reports of ICON , reports of ICON 20082008, Pisani & Assoc., , Pisani & Assoc., 2008 2008 & & 20122012; ; LA OOC file # LA OOC file # 007007--007007, reports of Pisani & Assoc., , reports of Pisani & Assoc., 2010 2010 & & 20152015))

Wilcox & Pan Am Pit Areas, 1974Wilcox & Pan Am Pit Areas, 1974

Wilcoxpit

PA pit

(oil wells in green, SWD wells in blue)(oil wells in green, SWD wells in blue)

Pan Am Pit Area, GW Data Ranges (in mg/l) Pan Am Pit Area, GW Data Ranges (in mg/l) from from 20102010--20152015

(data from LA OOC, Tillman file #007-007, Pisani & Assoc. reports 2012-2015)

Pan Am Pan Am Pit Area, Pit Area, Iron & Chloride Iron & Chloride Boundaries if Related to PitBoundaries if Related to Pit

Pan Am Pit Area, ORP & GW ElevationPan Am Pit Area, ORP & GW Elevation

2010 – 2015 data

Pan Am Pit GWPan Am Pit GW20102010--20142014

–– Higher iron w/ Higher iron w/ chlorides under pit; chlorides under pit; probable oilfield water probable oilfield water probable oilfield water probable oilfield water source impactsource impact

–– Higher arsenic w/Higher arsenic w/chlorides under chlorides under pit, probable oilfield pit, probable oilfield water source impactwater source impact

Pan Am Pit GWPan Am Pit GW20102010--20142014

–– As vs. FeAs vs. Fevaries in relation to pitvaries in relation to pitproximityproximity

–– ORP v. FeORP v. FeThere is not an obvious There is not an obvious relationship between relationship between ORP variability and FeORP variability and Fe

Applegate LeaseApplegate Lease

–– Pisani (2008, 2015) Pisani (2008, 2015) contours 250 mg/l contours 250 mg/l chloride (yellow line)chloride (yellow line)

–– I labeled highest I labeled highest –– I labeled highest I labeled highest dissolved arsenic hits dissolved arsenic hits over 0.10 mg/l (2006over 0.10 mg/l (2006--2015 data)2015 data)

–– Occurs In SWD &Occurs In SWD &tank battery pit areastank battery pit areas

(Pisani 2008, 2015 chloride contour maps From reports in LA OOC file #006-007)

Applegate Pit Area, GW Analyses Applegate Pit Area, GW Analyses (in mg/l) from 2006(in mg/l) from 2006--0707

(ICON analyses plotted on ICON base map, 1974 aerial; LA OOC Tensas-Poppadoc hearing, ICON 2008 report)

Applegate PitApplegate Pit

–– GeosyntecGeosyntec GW data, April GW data, April of 2008 (only ORP data of 2008 (only ORP data acquired)acquired)

–– Sampled six months after Sampled six months after partial pit partial pit digoutdigout/new /new fill, and during high GW fill, and during high GW elevation, reverse GW elevation, reverse GW elevation, reverse GW elevation, reverse GW movement towards the lakemovement towards the lake

–– If apparent As relationships If apparent As relationships with with ORPORP and Fe…and Fe…

–– Then apparent relationship Then apparent relationship of ORP and conductivity of ORP and conductivity (salinity) ? (salinity) ?

Applegate Pit Area, GW Data Ranges (in Applegate Pit Area, GW Data Ranges (in mg/l) from mg/l) from 20082008--20152015

Data from OOC Poppadoc file # 006-007; Geosyntec Report, 2008, Pisani 2012-2015

Applegate PitApplegate Pit

–– All data, 2007All data, 2007--15 (no 15 (no ORP except 2008)ORP except 2008)

–– The 2008 data are The 2008 data are generally lower values generally lower values compared to 2007 and compared to 2007 and compared to 2007 and compared to 2007 and 20122012--1515

–– The April 2008 sampling The April 2008 sampling was 6 months after pit rewas 6 months after pit re--closure & during high GW closure & during high GW and river elevations (GW and river elevations (GW flow away from river)flow away from river)

–– MWMW--3 has elevated 3 has elevated Fe, why?Fe, why?

Patterns & Interpretations: Patterns & Interpretations: ConclusionsConclusions

GW under the Pan Am pit moderately reduced, but no clear GW under the Pan Am pit moderately reduced, but no clear relation of ORP relation of ORP with As and Fewith As and FeAreas of oily waste impacts do not always have elevated AsAreas of oily waste impacts do not always have elevated AsHigh High Fe values (interpreted as added) Fe values (interpreted as added) with with elevated elevated arsenic arsenic and associated and associated ClCl indicate oilfield impactsindicate oilfield impactsOther Fe sources besides soil available (produced Other Fe sources besides soil available (produced water, rusty old water, rusty old flowlinesflowlines, etc), etc)Other Fe sources besides soil available (produced Other Fe sources besides soil available (produced water, rusty old water, rusty old flowlinesflowlines, etc), etc)Arsenic corrosion inhibitor usage in the Arsenic corrosion inhibitor usage in the 19501950s likely source of s likely source of elevated dissolved arsenic in elevated dissolved arsenic in studied pits studied pits at LSJ at LSJ fieldfieldIn addition, arsenicIn addition, arsenic--based herbicides & rust inhibitors possibly based herbicides & rust inhibitors possibly used in the past around oilfield facilitiesused in the past around oilfield facilities——this usage and its this usage and its modern impacts usually not consideredmodern impacts usually not consideredThe The GeosyntecGeosyntec 2008 2008 reductivereductive--dissolution model dissolution model for for elevated elevated GW arsenic & GW arsenic & iron below pits iron below pits is not supported is not supported by by additional additional data; plus, data; plus, based on onebased on one--time sampling of ORP, As & Fe (six time sampling of ORP, As & Fe (six months after pit closure)months after pit closure)

A Possible ModelA Possible Model

Observed ion mobility in GW from PA pit: Cl > Fe > AsObserved ion mobility in GW from PA pit: Cl > Fe > AsHFOs added to emergency pits from produced water HFOs added to emergency pits from produced water over decades; As usage in 1950s, strongly absorbed by over decades; As usage in 1950s, strongly absorbed by HFOs when presentHFOs when presentIn pit bottom, oily sludge and sometimes stagnant In pit bottom, oily sludge and sometimes stagnant saltwater above this, reducing; GW below reducingsaltwater above this, reducing; GW below reducingIn pit bottom, oily sludge and sometimes stagnant In pit bottom, oily sludge and sometimes stagnant saltwater above this, reducing; GW below reducingsaltwater above this, reducing; GW below reducingMovement of reducing water with Cl, Fe (Movement of reducing water with Cl, Fe (++ As) where pit As) where pit seepage, into sediment with Fe grain coatings seepage, into sediment with Fe grain coatings GW away from pit more oxidizing, see Fe frontGW away from pit more oxidizing, see Fe frontAdded As stays within or close to pit or source originsAdded As stays within or close to pit or source originsOne monitor well (MWOne monitor well (MW--3) in Applegate area has elevated 3) in Applegate area has elevated Fe (and possibly As) that is not related to the pit; the Fe Fe (and possibly As) that is not related to the pit; the Fe is a clue that another source is responsibleis a clue that another source is responsible

Selected ReferencesSelected References

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