GJ

Review
http://dx.doi.org/10.1007/s12303-017-0010-z
pISSN 1226-4806 eISSN 1598-7477 Geosciences Journal

Analytical methods for geochemical monitoring of CO2

capture and storage sites
Seulki Jeong, Hyun A Lee, and Hye-On Yoon*
Seoul center, Korea Basic Science Institute, 6-3, Inchon-ro 22-gil, Seongbuk-gu, Seoul 02855, Republic of Korea

ABSTRACT: CO2 leakage monitoring is essential to ensure the environmental safety for CO2 capture and storage (CCS) technologies. This
study aims to provide recommendations for the selection of analytical methods for monitoring of geochemical parameters at CCS
sites. Five CCS sites are reviewed to investigate the changes in geochemistry following CO2 leakage. The following geochemical parameters were
determined for monitoring CCS sites: alkalinity, electrical conductivity (EC), pH described as geochemical factors, and Ba, Ca, Fe, K, Mg,
Mn, and Na contents, referred to as elements in this study. The international analytical methods provided by ISO, USEPA, and USGS, which
are commonly used, are first compared, followed by. The considerations for selection of CCS-site-specific analytical methods were
suggested, the water sample characteristics, recommended ranges, required equipment, and significant interference.
Key words: analytical methods, CO2 capture and storage, CO2 leakage geochemical monitoring

Manuscript received October 3, 2016; Manuscript accepted January 10, 2017

1. INTRODUCTION CO2 produced by various industrial processes, (2) compressing

and transporting the captured CO2, and then (3) injecting the
The emission of atmospheric carbon dioxide (CO2) has become CO2 into a sequestration site, such as selected geological reservoirs
a major concern because of its adverse impact on global or oceans, for storage (Kheshgi et al., 2012).
warming and climate change (Leung et al., 2014; Miller, 2015). Although CCS technologies are expected to play important
Global atmospheric CO2 levels have increased steadily over roles in climate change mitigation, the environmental safety
the past decades to a record of ~ 400 ppm, the global monthly of underground CO2 storage sites, and the impact of CO2 leakage is
mean level recorded in Nov 2015 (NOAA, 2015). Compared still being addressed (Elzahabi and Yong, 2001; Bijma et al.,
to 2010 levels, CO2 emissions must be reduced globally, by 2013; Leung et al., 2014). Therefore, for the verification of CO2
41–72% by 2050 and by 78–118% by 2100, to avoid the worst storage integrity, CO2 leakage monitoring has recently attracted
effects of global warming (IPCC, 2013; Leung et al., 2014). much attention (Hovorka, 2008; Opedal et al., 2014; Mito et
Several regions have participated in the reduction of CO2 al., 2015). Various monitoring technologies have been examined
emissions, including Europe (Eurostat, 2015), USA (USDOS, for investigating CO2 leakage from storage sites into the surrounding
2014), China (Xu et al., 2015) as well as Korea (South Korea, environment that includes, the atmosphere, soil, and groundwater.
2000). The most effective way to reduce CO2 emissions is through The direct measurement of CO2 fluxes across soil-atmosphere
the use of clean fuels, renewable energy, and nuclear power, and water-atmosphere boundaries is one of the most effective
instead of conventional fossil fuels. Since these alternative energy ways to monitor CO2 storage sites (Pokryszka et al., 2010; Bastviken
sources have some limitations (Kargbo et al., 2010), CO2 capture et al., 2015). To detect changes in the underground geology of
and storage (CCS) has been regarded as an alternative emerging storage sites caused by CO2 release, CO2 leakage can be indirectly
technology. CCS technology has three main steps: (1) capturing monitored by a variety of techniques including: seismic
monitoring (Verkerke et al., 2014), geoelectrical methods (Kiessling
*Corresponding author: et al., 2010), gravimetric methods (Leung et al., 2014), and
Hye-On Yoon
Seoul center, Korea Basic Science Institute, 6-3, Inchon-ro 22-gil, Seongbuk- geochemical monitoring (Bielinski et al., 2008; Kharaka et al.,
gu, Seoul 02855, Republic of Korea 2010; Jenkins et al., 2012; Jones et al., 2014). Among these
Tel: +82-2-6943-4192, Fax: +82-2-6943-4149, E-mail: dunee@kbsi.re.kr monitoring techniques, time-dependent changes in geochemical
The Association of Korean Geoscience Societies and Springer 2017 records, such as pH, trace elements, and heavy metals, provide
2 Seulki Jeong, Hyun A Lee, and Hye-On Yoon

some of the most compelling evidence, and warning, of any were recorded. Analyses of total inorganic carbon (TIC)/total
seepage that requires mitigating action (Solomon, 2007). Therefore, organic carbon (TOC), major cations, anions, and trace elements
the selection of geochemical parameters and appropriate were also performed. A site-specific analysis was also conducted at
analytical methods should be significant to verify CO2 leakage at a CO2-enhanced oil recovery site located in western Texas,
CCS sites shortly. USA (Romanak et al., 2012). This field research focused on
This study covers the analytical considerations for geochemical monitoring carbonate-specific geochemical factors, such as
monitoring at CCS sites to assure environmental integrity against dissolved inorganic carbon (DIC), alkalinity, pH, Ca, and
CO2 leakage. The objectives of this study are to (1) investigate HCO3–, due to calcite dissolution mainly caused by CO2 input
the geochemical parameters to be analyzed through five field into an aquifer. According to the report of Trautz et al. (2013),
studies, (2) determine the major monitoring parameters, and a field study was initiated to investigate the potential
(3) make some recommendations for the selection of analytical environmental impact and to collect geochemical and hydrologic
methods for the monitoring of CCS sites. The analytical methods data in response to dissolved CO2 injection. A dissolved CO2
for each determined geochemical parameter were compared release experiment was performed at Plant Daniel in Jackson
for their applicable matrix, detection limit, and equipment. County, MS, USA, from October 2011 to March 2012.
This comparison of analytical methods was conducted using Hydrogeological and geochemical parameters (e.g., pH, total
widely used international methods, such as International dissolved solids, EC, alkalinity, major cations, minor cations,
Organization for Standardization (ISO) and widely used methods and chloride) were characterized in shallow groundwater and
provided by the US Environmental Protection Agency (USEPA) sediment samples (Trautz et al., 2013). The last experimental
and US Geological Survey (USGS). site is located in the Svelvik Ridge in Oslo, Norway, where
CO2 migration and leakage were monitored (Humez et al.,
2. DETERMINATION OF GEOCHEMICAL 2014). After 1.67 t of CO2 was injected into the surface over six
PARAMETERS FOR THE MONITORING OF CCS days, the chemical parameters in environmental samples,
SITES: A FIVE-SITE STUDY including soil and water, were monitored. The temperature,
pH, and EC of the groundwater, as well as major, minor, and
This study reviewed five CCS sites to determine the geochemical trace elements (Ca, Na, Mg, Al, Ba, Mn, Ni, Co, and B), and
parameters for the monitoring of CO2 storage sites. A series some isotopes, were measured.
of CO2 injection experiments were performed to investigate The geochemical parameters measured at these five sites are
potential CO2 leaks and evaluate near-surface monitoring with listed in Table 1. Similar changes in some geochemical parameters
detection techniques for each CO2 storage site. Geochemical in response to CO2 injection or leakage, were found among
parameters to be monitored for the prediction of potential the five sites. Following CO2 injection, calcite and dolomite
CO2 leakage at each site were compared in this study. Among (or Mg-rich calcite) dissolution occurred, leading to a decrease
them, the most monitored parameters for the investigation of in pH and an increase in alkalinity as the levels of HCO3–, and
geochemical changes in CO2 flux, were determined. The first site, carbonate minerals such as Ca and Mg, increased. The major
located in Bozeman, MT, USA, was developed by the Zero and trace cations (e.g., Na, Ca, Ba, Fe, Mn, and Cr) were
Emission Research and Technology Center (ZERT) to study generally observed to increase in concentration. The increases in
near-surface CO2 transport and detection technologies (Spangler et cation concentrations are likely to be caused by desorption-
al., 2009). During 2007 and 2008, several soils and water were ion exchange reactions with H+, Ca2+ and Mg2+ (Kharaka et
sampled to investigate changes in geochemistry due to CO2 al., 2010), and the desorption/co-dissolution of cations bound to
injection or leakage. Water level, temperature, pH, alkalinity, the surface or in the structure of minerals accompanied by
electrical conductivity (EC), and dissolved oxygen (DO) were the dissolution of minerals, such as silicates that result from
measured. Major and trace solutes, including HCO3–, Na, K, the low pH caused by CO2 injection (Humez et al., 2014). In
Mg, Ca, As, B, Cd, Cr, Cu, Fe, Mn, Pb, Se, U, and Zn, were also contrast, typical anion concentrations, like chloride (Cl), did
analyzed (Kharaka et al., 2010). CO2 injection experiments not respond consistently to CO2 injection. Several studies
were also conducted at a former military airfield near Wittstock, found that major anions (e.g., sulfate and chloride) decreased
Brandenburg, Germany. Approximately 400,000 L of CO2 were at CO2 storage sites (Peter et al., 2012; Dethlefsen et al., 2013);
injected into a shallow aquifer to simulate a CO2 leakage scenario the anion concentrations also exhibited no significant trends
at a field site (Schulz et al., 2012). At this site, groundwater at the CCS sites reviewed in this study. From these results, several
samples were collected and site parameters such as pH, temperature, monitoring parameters for ensuring CO2 storage integrity
oxygen concentration, EC, alkalinity, and redox potential were determined, are listed in bold in Table 1. Some carbonate

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 Analytical methods for geochemical monitoring of CCS sites 3

Table 1. Monitoring parameters measured at five CO2 capture and storage sites
CO2 storage site
Parameters Bozeman, USA (Spangler et Wittstock, Germany Western Texas, USA Jackson County, USA Oslo, Norway
al., 2009; Kharaka et al., 2010) (Schulz et al., 2012) (Romanak et al., 2012) (Trautz et al., 2013) (Humez et al., 2014)
pH O O O O O
EC O O O O O
alkalinity O O O O O
DO O O O
TDS O O
DIC O
Sodium (Na) O O O O
Potassium (K) O O O O O
Calcium (Ca) O O O O O
Magnesium (Mg) O O O O O
Barium (Ba) O O O O O
Aluminum (Al) O O
Arsenic (As) O O
Cadmium (Cd) O O
Copper (Cu) O
Iron (Fe) O O O
Manganese (Mn) O O O O O
Molybdenum (Mo) O O O
Lead (Pb) O
Selenium (Se) O O
Zinc (Zn) O O
TIC/TOC O
Nickel (Ni) O O
Cobalt (Co) O O O
Boron (B) O O
Lithium (Li) O O
Uranium (U) O O O
Bicarbonate (HCO3-) O O
Silicon (Si/SiO2) O O O
The determined parameters in this study are represented in bold.

parameters, such as pH, alkalinity, Ca, and Mg may be the classed as elements. Methods commonly used for the analysis
most suitable for detecting early CO2 leakage, due to their of selected geochemical parameters, as suggested by ISO,
immediate reactions with CO2. EC, widely used as a general USEPA, and USGS for water samples, are first introduced.
indicator, was determined due to its direct correlation with The general analytical methods reviewed throughout this
bulk changes in the total concentration of dissolved cations study are listed in Appendices 1 (geochemical factors) and 2
and anions (Hubert and Wolkersdorfer, 2015). Major cations (elements). The applicable concentration range or detection
(e.g., Na, K, Fe, Ba, and Mn) were also selected. limit, recommended matrices, equipment, and major source
of interference of each analytical method are compared. It
3. Analytical methods for monitoring param- should be noted that analytical methods suggested by ISO are
eters at CO2 storage sites reviewed every five years, while the latest review dates for the
USEPA and USGS methods are addressed in this study.
In this study, a comparison of the official analytical methods
provided by ISO, USEPA, and USGS, for monitoring the 3.1. Comparison of Analytical Methods for Geo-
parameters determined above, was performed. The determined chemical Factors in Water
monitoring parameters were classified into two groups, geochemical
factors and elements. Geochemical factors included pH, A total of 13 analytical methods for selected geochemical
alkalinity, and EC, while Ba, Ca, Fe, K, Mg, Mn, and Na were factors including alkalinity, EC, and pH, in water samples are

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4 Seulki Jeong, Hyun A Lee, and Hye-On Yoon

listed in Appendix Table A1. Four analytical methods are sodium errors at pH > 10, grease, fine, and heavy particulate
suggested for the analysis of alkalinity in water samples: ISO matter, and temperature.
9963-1:1994, EPA 310.1, EPA 310.2, and USGS I-2030-85.
Titration using indicators, methyl orange for a pH 4.5 endpoint 3.2. Comparison of Analytical Methods for Selected
and phenolphthalein for a pH 8.3 endpoint, is mainly used to Elements in Water
determine alkalinity, with a shifting pH endpoint analyzed by
a pH meter or an automatic titrator. The main difference among Analytical methods for the monitoring of selected elements
the four methods is the applicable range of alkalinity. The at CO2 storage sites are shown in Appendix Table A2; these
determination of alkalinity by EPA 310.1 and USGS I-2030- methods are categorized by element. The analytical equipment,
85 can be used for water of any alkalinity, while ISO 9963- applicable matrices, and method detection limits (MDLs) are
1:1994 and EPA 310.2 are only used for waters of alkalinities significantly different in each international analytical method
ranging from 0.4–20 mmol/L and 10–200 mg/L for CaCO3. provided by ISO, USEPA, and USGS. ISO 14911:1998, entitled
Turbid samples should be filtered prior to analysis because “determination of dissolved Li+, Na+, NH4+, K+, Mn2+, Ca2+,
turbidity generally caused interference. EPA 310.2 is mentioned Mg2+, Sr2+, and Ba2+ using ion chromatography”, can be applied
as not being available for alkalinity analysis of filtered water to the analysis of most elements targeted in this study, except
samples used for National Pollutant Discharge Elimination for Fe. When using ion chromatography (IC), the optimum
System (NPDES) monitoring. The international analytical methods concentration ranges for dissolved cations is 1–100 mg/L for
for EC measurements are provided by ISO and USGS. The Ba, 0.5–50 mg/L for Ca, 0.1–10 mg/L for K, 0.01–1 mg/L for
ISO 7888:1985 and USGS I-1780-85/I-2781-85 methods are Li, 0.5–50 mg/L for Mg, 0.5–50 mg/L for Mn, and 0.1–10 mg/L
specified for the measurement of EC of all types of water and for Na. The method suggested in ISO 11885:2007 is useful for
all EC values using conductivity instruments. USGS NFM determining the total content of dissolved cations for all elements
6.4.3.A-SW/NFM and 6.4.3.B-GW/NFM.6.4.3.C are intended selected in this study. Inductively coupled plasma optical emission
for the measurement of the EC of surface and groundwater, spectrometry (ICP-OES) is utilized to analyze elements in ground,
from fresh to saline, with the specific measured range of 50– surface, raw, potable, and wastewater samples. The MDL of
50,000 S/cm. To prevent interference in EC analysis, filtration each element is not referred to, so the optimum concentration
is essential for water samples containing suspended materials. ranges should be determined specifically by considering the
In the case of water pH measurements, six analytical methods instrumental detection limits (IDL) of ICP-OES. ISO 17294-
are recommended. ISO 10523:2008, entitled “determination 2:2003 can be used to measure 62 elements, using inductively
of pH”, determines the pH of all kinds of water, including rain, coupled plasma mass spectrometry (ICP-MS), including all
drinking, mineral, bathing, surface, ground water, municipal/ selected elements in drinking, surface, groundwater, wastewater,
industrial wastewater, and liquid sludge. Unlike the other and eluates. Since every element of interest has an isotope, the
methods, this method is recommended for waters in the pH MDL of the most abundant isotope was selected. For Ca
range 2 to 12, with ionic strength less than 0.3 mol/kg at a concentration determination, two additional methods have
temperature of 0–50 °C. The pH determination methods provided been announced by ISO, ISO 6058:1984 and ISO 7980:1986.
by USEPA are divided into three categories according to purpose. ISO 6058:1984 describes a titrimetric method using
The most general method is EPA 150.1, used for drinking, ethylenediaminetetraacetic acid (EDTA), for the determination
surface, and saline waters, and EPA 150.2 should be selected of the Ca2+ contents of ground, surface, drinking, and municipal/
for continuous electrometric pH monitoring. It is important industrial raw water. This titration method cannot be applicable
to find the contacting point representative of total continuous to water with a high salt concentration, such as seawater, and
water flow. The last EPA method for pH determination is can be used for Ca2+ concentrations ranging from 2 to 100
EPA 9040B, which is used for aqueous waste, with a ratio of mg/L. ISO 7980:1986 is applicable to measuring dissolved Ca
aqueous phase at least 20% of the total volume of the waste as well as Mg content by flame atomic absorption spectrometry
and with low salinity (<0.1 M solution). The USGS also provides (Flame AAS). When using an air/acetylene flame and a 10:1
many methods for water pH measurement. USGS I-1586/I- dilution factor, the optimum applicable range is 3–50 mg/L
1586-85/I-2587-85 are considered for pH determination in for Ca and 0.9–5 mg/L for Mg in raw and drinking water. For
most kinds of water samples, whereas USGS NFM 6.4.3.A- determining Fe concentration, a spectrometric method using
SW/NFM 6.4.3.B-GW/NFM.6.4.3.C are recommended as 1,10-phenanthroline is also used (ISO 6332:1988). The recommended
methods for surface and groundwater, from fresh to saline. concentration range is 0.01–5 mg/L of Fe. This method is
The common interference factors for pH measurements are unsuitable for water containing Cu2+, Co2+, Cr6+, and Zn2+

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 Analytical methods for geochemical monitoring of CCS sites 5

concentrations greater than ten times the iron concentration, in excess of 30 mg/L. The last international method provided
or Ni2+, Ag2+, and Ca2+ concentrations of up to 2 mg/L, 1 g/L and by USEPA is EPA 200.9, entitled “determination of trace
50 mg/L, respectively, due to interference. ISO 6333:1986, is a elements by stabilized temperature graphite furnace atomic
specific method for analyzing total Mn2+, including dissolved, absorption”. This method deals with the determination of Fe
suspended, and organically bound manganese in surface and and Mn concentrations in water samples including ground,
drinking water, using a formaldoxime spectrometric method. surface, drinking water, storm runoff, industrial/domestic
The optimum concentration range is 0.01–5 mg/L of Mn, hence, wastewater, sediment, sludge, and soil. The dissolved and total
highly contaminated water is not recommended. Certain content recoverable concentrations of Fe and Mn are determined by
ranges of Fe, Co, Ca, Fe, and Mg in water samples can also graphite furnace atomic absorption (GFAA). Only the MDL
interfere with the accurate measurement of Mn. of Mn is represented as being below 0.3 g/L.
USEPA provides EPA 200.5, for determining the total USGS I-4471-97, a method entitled “determination of elements
concentration (i.e., dissolved and suspended fractions) of Ba, in whole-water digests using inductively coupled plasma-optical
Ca, Mg, Mn, and Na in drinking water samples using ICP- emission spectrometry and inductively coupled plasma-mass
OES. The MDLs are 0.05 g/L for Ba, 3.3 g/L for Fe, and 0.06 spectrometry”, is reported for determining 26 elements, including
g/L for Mn. In this method, amounts in excess of 125 or 250 Ba, Ca, Fe, Li, Mg, Mn, and Na. Both ICP-OES and ICP-MS
mg/L of the combined contents of Ca, Mg, and Na or SiO2 in can be used to determine Ba, Li, and Mn contents in natural
samples result in interference. EPA 200.7, entitled “trace elements whole-water digested using an in-bottle procedure, whereas
in water, solids, and biosolids by inductively coupled plasma- Ca, Fe, Mg, and Na concentrations are only recovered by ICP-
atomic emission spectrometry” uses ICP-OES to confirm the OES in this method. A relatively new analytical technique for
concentration of dissolved elements in water samples. This aqueous matrices including natural water, whole water, biota,
method targets all selected elements in this study, but total sediment, and soil digestates has been developed (i.e., USGS
dissolved solids (TDS) should be kept below 0.2% (w/v) to I-2020-05/I-4020-05). In this method, analyse carried out to
reduce potential interference. Although EPA 6010C is similar determine Ca, Fe, K, Mg, Na, and Si concentrations using collision/
to EPA 200.7 in terms of applicable equipment (i.e., ICP-OES) reaction cell technology implemented ICP-MS (cICP-MS) to
and elements (i.e., all elements targeted in this study), the reduce molecular ion interference. The MDLs for Ca, Fe, K,
applicable matrices are expanded in the former to any solution, Mg, Na, and Si are below 0.04, 1.0, 0.007, 0.009, 0.09, and 0.03
including groundwater. With the exception of groundwater mg/L, respectively. In the case of Ba, Ca, Fe, Mg, Mn, and Na,
samples, all aqueous samples need acid digestion prior to the analytical methods are divided into several categories
analysis. EPA 200.8 is also available for the determination of depending on their chemical forms, although they used the
concentrations of dissolved Ba and Mn in ground, surface, same equipment. The USGS method, entitled “barium, atomic
drinking water, wastewater, and sludge. The MDL of the ion- absorption spectrometric, direct”, is composed of four methods.
monitoring mode of ICP-MS is recommended to be 0.04 μg/L Among them, the method for determining the dissolved (I-
of Ba and 0.02 μg/L of Mn. When operating the ICP-MS in 1084-85) and total recoverable (I-3084-85) concentrations of
scanning-mode, a higher MDL is recommended that that for Ba might be applicable for the analysis of water samples
the selection ion-monitoring mode. EPA 208.1 and 208.2 having 100–5,000 μg/L of Ba. Similar to Ba, various chemical
concern the approved protocol for the analysis of Ba2+ following the forms of Ca, Fe, K, Li, Mg, and Mn in water and brine samples
NPDES (National Pollutant Discharge Elimination System) can also be determined. The optimum analytical ranges for
and SDWA (Safe Drinking Water Act). Atomic absorption (AA) dissolved or total recoverable elements in samples are: 0.01–
with direct aspiration and furnace techniques, is utilized, with 60 mg/L for Ca in USGS I-1152-85/I-3152-85, 10–1,000 g/L
recommended concentration ranges of 1–20 and 10–200 mg/L for Fe in USGS I-1381-85/I-3381-85, 0.01–10.0 mg/L for K in
of Ba for EPA 208.1 and 208.2, respectively. For Ca, Fe, K, Mg, USGS I-1630-85/I-3630-85, 10–1000 g/L for Li in USGS I-
Mn, and Na, there are designated NPDES methods in EPA 1425-85/I-3425-85, 0.01–50 mg/L for Mg in USGS I-1447-85/
215.1/215.2, 236.1/236.2, 258.1, 242.1, 243.1/234.2, and 273.1, I-3447-85, 10–1,000 g/L for Mn in USGS I-1454-85/I-3454-
respectively. These methods divide analyte into three categories 85, and 0.01–80 mg/L for Na in USGS I-1735-85/I-3735-85.
by their chemical forms: total, dissolved, and suspended. USGS provides two more analytical methods for measuring
Most of these methods use AA equipment, and titration with the Mn content in water matrices. The first (USGS I-1455-85),
EDTA is only applied in EPA 215.2 for the measurement of entitled “manganese, atomic absorption spectrometric, graphite
Ca. Interference during precision analysis using the titrimetric furnace”, suggests an analytical procedure for 0.2–12 g/L
method can be caused by Sr2+, Mg2+ and Ba2+, and alkalinity concentrations of Mn in low ionic-strength water with low

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 6
Table 2. Selected analytical methods for the determination of geochemical factors in water samples at CCS sites
Last
Factors Analytical Methods Title Matrix Applicable range Unit Equipment
reviewed
Drinking, surface, saline waters, domestic, and All ranges of
EPA 310.1 Alkalinity (Titrimetric, pH 4.5) – Titration 1978
industrial wastes alkalinity
Alkalinity

http://dx.doi.org/
EPA 310.2 Alkalinity (Colorimetric, Auto- Drinking, surface, saline waters, domestic, and 10–200 mg/L Autoanalyzer 1974
mated, Methyl Orange) industrial wastes as CaCO3
Field Measurements –
USGS NFM 6.3.3. A-SW, Any kind of conductiv-
EC Specific Electrical Conductance, Surface and groundwater from fresh to saline 50–50,000 μS/cm 2005
NFM 6.3.3. B-GW ity instruments
Version 1.2
Rain, drinking and mineral waters, bathing water, pH meter
ISO 10523:2008 Determination of pH surface and groundwater, as well as municipal and 2–12 – 2012
(glass electrode)
industrial waste water, and liquid sludge
Drinking, surface, and saline waters, domestic and pH meter
EPA Method 150.1 pH (Electrometric) – – 1982
pH industrial wastes, and acid rain (glass electrode)
EPA Method 150.2 pH, Continuous Monitoring Drinking, surface, and saline waters, domestic and – – pH meter 1982
(Electrometric) industrial waste waters (glass electrode)
USGS NFM 6.4.3.A-SW, NFM Field Measurements – pH, Ver- pH meter
Surface and groundwater, from fresh to saline – – 2006
6.4.3.B-GW, NFM.6.4.3.C sion 1.3 (glass electrode)

Table 3. Selected analytical methods for the determination of elements in water samples at CCS sites
Applicable concentra- Last
Methods Elements Title Matrix Unit Equipment
tion range reviewed
ISO 11885:2007 Ba, Ca, Fe, K, Determination of selected elements by inductively Ground, surface, raw, potable, and waste water – – ICP-OES 2011
Mg, Mn, Na coupled plasma optical emission spectrometry (ICP-
OES)
ISO 17294-2:2003 Ba, Ca, K, Mg, Application of inductively coupled plasma mass spec- Drinking water, surface water, groundwater, >0.5 (Ba), >50 (Ca) g/L, mg/L ICP-MS 2009
Mn, Na trometry (ICP-MS) – Part 2: Determination of 62 elements wastewater, and eluates >50 (K), >1 (Mg) mg/L, mg/L
>3 (Mn), >10 (Na) mg/L, mg/L
ISO 6058:1984 Ca Determination of calcium content – EDTA titrimetric Ground, surface and drinking, municipal, and 2–100 mg/L Titration 2012
method industrial raw water
EPA 6010C Ba, Ca, Fe, K, Inductively coupled plasma-atomic emission spec- Any solution (groundwater, all aqueous, and >IDL μg/L ICP-OES
Mg, Mn, Na trometry solid matrices after digestion)
EPA 200.8 Ba, Mn Determination of trace elements in waters and wastes Groundwater, surface waters, drinking water, >0.04 μg/L ICP-MS 1994
Seulki Jeong, Hyun A Lee, and Hye-On Yoon

by inductively coupled plasma-mass spectrometry wastewaters, sludge, and soil samples

EPA 200.9 Fe Determination of trace elements by stabilized tem- Groundwater, surface waters, drinking water, – – AAS –
perature graphite furnace atomic absorption storm runoff, industrial and domestic wastewa-
ter, sediment, sludge, and soil
USGS I-1152-85, Ca Calcium, atomic absorption spectrometric, direct Atmospheric precipitation, water, brine, and 0.01–5.0 mg/L, AAS –
I-3152-85, I-5152-85, water-suspended sediment 1.0–60, mg/L
I-7152-85 10 mg/kg
USGS I-1630-85, K Potassium, atomic absorption spectrometric, direct Atmospheric precipitation, water, brine, and 0.01–1.0 mg/L AAS –
I-3630-85, I-5830-85 water-suspended sediment 0.1–10.0 mg/L
10 mg/kg
USGS I-1447-85, Mg Magnesium, atomic absorption spectrometric, direct Atmospheric precipitation, water, brine, and 0.01–5.0 mg/L AAS –
I-3447-85, I-5447-85, water-suspended sediment 2.5–50 mg/L
I-7447-85 10 mg/kg
USGS I-1456-85 Mn Manganese, atomic absorption spectrometric, chela- Water, brine 1–100 μg/L AAS –
tion-extraction
USGS I-1735-85, Na Sodium, atomic absorption spectrometric, direct Atmospheric precipitation, water, brine, and 0.01–1.0 mg/L AAA –
I3735-85, I5735-85 water-suspended sediment. 0.1–80 mg/L
10 mg/kg

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 Analytical methods for geochemical monitoring of CCS sites 7

precipitation. In the other method (USGS I-1456-85), 1–100

g/L of Mn in water and brine is analyzed by AAS following
chelation with ammonium pyrrolidine dithiocarbamate (APDC)
and extraction with chloroform.

4. RECOMMENDATIONS: SELECTION OF ANA-

LYTICAL METHODS FOR MONITORING FACTORS
IN WATER MATRICES AT CCS SITES

The widely used international analytical methods provided

by ISO, USEPA, and USGS are compared in chapter 3. Since
the method used depends on the characteristics of the water
sample, applicable range, and equipment, not all methods can
be applied to the analysis of geochemical parameters and CCS
site monitoring. For example, whether the sample is groundwater Fig. 1. A comparison of the recommended applicable ranges of ana-
or brine can influence the selection of the analytical method. lytical methods for selected geochemical factors in water samples: (a)
Moreover, sample dilution can lead to analysis errors, so an alkalinity, (b) EC, and (c) pH. The solid lines indicate the specific
working range for each method, and the methods that cover the
analytical method with an applicable range that is close to the entire range of the analyte are represented as dotted lines with dou-
expected concentration range, should be selected. Groundwater ble-headed arrows. The detection limits of the method and instru-
sampled from practical CO2 sequestration sites can be divided ment are shown as short arrows that commence from solid lines.
into two types, fresh groundwater related to shallow groundwater
test sites and deep brine water related to oil recovery. The When multiple elements need monitoring at the same time,
applicable analytical methods, for groundwater and brine are analytical methods using ICP-OES and ICP-MS, according to
listed in Tables 2 and 3. ISO 11885:2007 and EPA 200.8 (etc.), are preferable to methods
Several factors should also be considered when selecting an for single element determination, including AAS or titration,
analytical method for the determination of geological factors as seen in EPA 200.9, ISO 6058:1984, USGS I-1152-85 (etc.).
and elements (UNOCD, 2009), including the limit of detection Moreover, the method selection depends greatly on the
required, accuracy and precision, the number of samples to availability of operational equipment. This availability aspect
be analyzed, the equipment required, interference in samples, encompasses both physical possession of the equipment and
time, and cost (WHO, 2013). Figures 1 and 2 show schematic proficiency in terms of skillful operation that includes minimization
diagrams that compare of the recommended applicable ranges of equipment interference. An experienced operator can
of selected analytical methods for the monitoring of CCS obtain the reliable results required, especially by ICP-MS. The
sites. The applicable range should be predefined according to different types of inductively coupled plasma equipment (e.g.,
the purpose of the analysis in relation to predicted concentration ICP-OES and ICP-MS) have two main sources of interference:
or content, and the number of elements to be simultaneously isobaric interference caused by a shared common mass between
analyzed. For example, alkalinity can be measured using both different elemental isotopes, and polyatomic interference
EPA 310.1 and 310.2; however, beyond the range of 10–200 resulting from the combination of isotopes of different elements
mg/L for CaCO3, alkalinity can be only determined by EPA (Hsiung et al., 1997; May and Wiedmeyer 1998; Hirata 2004;).
310.1. In practical CCS test sites, alkalinity is generally measured to Since the detection limits and applicable ranges for elements
be at least 400 mg/L as HCO3–, during the injection test; hence, vary with the wavelength selected, spectrometer used, and
EPA 310.1 will be appropriate for these sites. The highest levels of matrices, the working range needs to be considered when choosing
Ca in the test sites exceeded 440 mg/L, while the lowest was 2 the analytical methods, which depends on the operational
mg/L. Meanwhile, concentrations of Na ranged between 7.2 conditions of each instrument.
and 74.1 mg/L, therefore, ISO 17294-2:2003 cannot be applied. To summarize, analytical method selection depends on
At the natural analogue site in New Mexico (Keating et al., various factors, and should be determined by considering key
2010), the concentration ranges of observed ions exceeded parameters, especially those regarding levels of contamination,
the results obtained from shallow-aquifer test sites (e.g., 0.2– the site-specific characteristics of the matrices being analyzed,
40.4 mg/L for K, <0.01–1.71 mg/L for Fe). For this site, ISO and the equipment available. This study provides some
11885:2007, EPA 6010C, and EPA 200.9 would be appropriate. recommendations for determining the site-specific analytical

http://www.springer.com/journal/12303 http://dx.doi.org/10.1007/s12303-017-0010-z
8 Seulki Jeong, Hyun A Lee, and Hye-On Yoon

Fig. 2. A comparison of the recommended applicable ranges of analytical methods for selected elements in water samples: (a) barium, (b)
calcium, (c) iron, (d) potassium, (e) magnesium, (f) manganese, and (g) sodium. The solid lines indicate the specific working range for each
method, and the methods that cover the entire range of the analyte are represented as dotted lines with double-headed arrows. The detection
limits of the method and instrument are shown as short arrows that commence from solid lines.

method for each geochemical parameter of interest at CO2 perature signals: Numerical investigation. International Journal of
monitoring sites, and contributes to monitoring technologies Greenhouse Gas Control, 2, 319–328.
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ACKNOWLEDGMENTS Dethlefsen, F., Köber, R., Schäfer, D., al Hagrey, S.A., Hornbruch, G.,
Ebert, M., Beyer, M., Großmann, J., and Dahmke, A., 2013, Moni-
This study was supported by the Integrated Environmental toring approaches for detecting and evaluating CO2 and formation
Management of Geologic CO2 Storage project (Grant code: water leakages into near-surface aquifers. Energy Procedia, 37,
2014001810001) of the Korea Environmental Industry & Technology 4886–4893.
Elzahabi, M. and Yong, R.N., 2001, pH influence on sorption character-
Institute (KEITI) and the Korean Ministry of Environment.
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 Analytical methods for geochemical monitoring of CCS sites 11

APPENDIX

Table A1. Analytical methods for determining geochemical factors in water samples provided by ISO, EPA, and USGS
Applicable
Factors Analytical methods Matrix Unit Equipment Last reviewed
range
ISO 9963-1:1994 Natural, treated, waste water 0.4–20 mmol/L Titration 2010
Drinking, surface, saline All ranges of
EPA 310.1 – Titration 1978
water alkalinity
Alkalinity Drinking, surface, saline mg/L as Autoanalyzer
EPA 310.2 10–200 1974
water CaCO3
All ranges of Automatic titrator with potentiometric
USGS I-2030-85 Water – –
alkalinity assembly, or, combination electrode
All ranges of S/m Flow- or dip-type conductivity cell fitted
ISO 7888:1985 Water with two or more electrodes or conductivity 2012
EC instruments with induction type electrodes
USGS I-1780-85, All natural, treated, industrial All ranges of Conductivity cell, conductivity meter,
EC – –
I-2781-85 water EC thermometer
USGS NFM 6.3.3. Surface, groundwater from
A-SW, NFM 6.3.3. 50–50,000 S/cm Any kind of conductivity instrument 2005
fresh to saline
B-GW
Rain, drinking, mineral,
bathing, surface, ground
ISO 10523:2008 2–12 – pH meter (glass electrode) 2012
water, municipal/ industrial
wastewater, liquid sludge
Drinking, surface, saline
EPA 150.1 – – pH meter (glass electrode) 1982
water, acid rain
Drinking, surface, saline
EPA 150.2 – – pH meter (glass electrode) 1982
water
pH
pH meter (glass electrode in combination
EPA 9040B Aqueous wastes – – with a reference potential or a combination –
electrode)
USGS I-1586, Any natural. treated water, – – pH meter (glass electrode) –
I-1586-85, I-2587-85 any industrial/wastewater
USGS NFM 6.4.3.A- Surface, groundwater from
SW, NFM 6.4.3.B- – – pH meter (glass electrode) 2006
fresh to saline
GW, NFM.6.4.3.C

Table A2. Analytical methods for determining selected elements in water samples provided by ISO, EPA, and USGS
Method detec- Last
Elements Analytical methods Matrix Unit Equipment
tion limit (MDL) reviewed
Ba ISO 14911:1998 Drinking, surface, wastewater 1–100(a) mg/L IC 2014
ISO 11885:2007 Ground, surface, raw, potable, wastewater >IDL – ICP-OES 2016
ISO 17294-2:2016 Drinking, surface, groundwater, wastewater, >3 g/L ICP-MS 2016
eluates
EPA 200.5 Drinking water >0.05 μg/L AVICP- OES 2003
EPA 200.7 Water, wastewater >0.001 mg/L ICP- OES 2001
EPA 6010C Any solution >IDL – ICP- OES 2000
EPA 200.8 Ground, surface, drinking, wastewater, >0.04 g/L ICP-MS 1994
sludge, soil
EPA 208.1 Water 1–20(a) mg/L AAS (direct aspiration) 1974
EPA 208.2 Water 10–200(a) g/L AAS (furnace technique) 1978
USGS I-4471-97 Whole-water >0.5 g/L ICP-OES, ICP-MS 2003
>0.08
USGS I-1084-85, Water 100–5,000(a) g/L AAS (direct aspiration) –
I-3084-85
Ca ISO 14911:1998 Drinking, surface, waste water 0.5–50(a) mg/L IC 2014
ISO 11885:2007 Ground, surface, raw, potable, waste water >IDL – ICP-OES 2016
ISO 17294-2:2016 Drinking, surface, groundwater, waste water, >10 g/L ICP-MS 2016
eluates

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12 Seulki Jeong, Hyun A Lee, and Hye-On Yoon

Table A2. (continued)

Method detec- Last
Elements Analytical methods Matrix Unit Equipment
tion limit (MDL) reviewed
(a)
Ca ISO 6058:1984 Ground, surface, drinking, municipal/indus- 2–100 mg/L Titration 2013
trial raw water
ISO 7980:1986 Raw, drinking water 3–50(a) mg/L Flame AAS 2012
EPA 200.5 Drinking water >IDL – AVICP- OES 2003
EPA 200.7 Water, wastewater >0.01 mg/L ICP- OES 2001
EPA 215.1 Water 0.2–7(a) mg/L AAS (direct aspiration) 1974
(a)
EPA 215.2 Drinking, surface water, domestic/industrial 0.5–25 mg/L as Titration 1978
wastes CaCO3
EPA 6010C Any solution >IDL – ICP- OES 2000
USGS I-4471-97 Whole-water >5 g/L ICP-OES 2003
USGS I-2020-05, Water, biota/sediment/soil digestates >0.04 mg/L cICP-MS 2006
I-4020-05
USGS I-1152-85, Water, brine 0.01–60(a) mg/L AAS (direct aspiration) –
I-3152-85
Fe ISO 11885:2007 Ground, surface, raw, potable, waste water >IDL – ICP-OES 2016
ISO 6332:1988 Water, waste water 0.01–5(a) mg/L Spectrometer 2012
EPA 200.5 Drinking water >3.3 g/L AVICP- OES 2003
EPA 200.7 Water, wastewater >0.03 mg/L ICP- OES 2001
EPA 6010C Any solution >IDL – ICP- OES 2000
EPA 200.9 Ground, surface, drinking water, storm run- >IDL – AAS (graphite furnace) 1994
off, industrial/domestic wastewater, sedi-
ment, sludge, soil
EPA 236.1 Water 0.3–5(a) mg/L AAS (direct aspiration) 1978
EPA 236.2 Water 5–100(a) g/L AAS (furnace technique) 1978
USGS I-4471-97 Whole-water >6 g/L ICP-OES 2003
USGS I-2020-05, Water, biota/sediment/soil digestates >1 g/L cICP-MS 2006
I-4020-05
USGS I-1381-85, Water 10–1,000(a) g/L AAS (direct aspiration) –
I-3381-85
K ISO 14911:1998 Drinking, surface, waste water 0.1–10(a) mg/L IC 2014
ISO 11885:2007 Ground, surface, raw, potable, waste water >IDL – ICP-OES 2016
ISO 17294-2:2016 Drinking, surface, groundwater, waste water, >50 g/L ICP-MS 2016
eluates
EPA 200.7 Water, wastewater >0.3 mg/L ICP- OES 2001
EPA 6010C Any solution >IDL – ICP- OES 2000
EPA 258.1 Water 0.1–2(a) mg/L AAS (direct aspiration) 1974
USGS I-2020-05, Water, biota/sediment/soil digestates >0.007 mg/L cICP-MS 2006
I-4020-05
USGS I-1630-85, Water, brine 0.01–10(a) mg/L AAS (direct aspiration) –
I-3630-85
Li ISO 14911:1998 Drinking, surface, waste water 0.01–1(a) mg/L IC 2014
ISO 11885:2007 Ground, surface, raw, potable, waste water >IDL – ICP-OES 2016
ISO 17294-2:2016 Drinking, surface, groundwater, waste water, >10 g/L ICP-MS 2016
eluates
EPA 200.7 Water, wastewater >0.001 mg/L ICP- OES 2001
EPA 6010C Any solution >IDL – ICP- OES 2000
USGS I-4471-97 Whole-water <8 g/L ICP-OES 2003
<0.04 ICP-MS
USGS I-1425-85, Water, brine 10–1,000(a) g/L AAS (direct aspiration) –
I-3425-85
USGS I-2477-92 Filtered/acidified natural water <0.03 g/L ICP-MS 1999
Mg ISO 14911:1998 Drinking, surface, waste water 0.5–50(a) mg/L IC 2014
ISO 11885:2007 Ground, surface, raw, potable, waste water >IDL – ICP-OES 2016
ISO 17294-2:2016 Drinking, surface, groundwater, waste water, >1 g/L ICP-MS 2016
eluates

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 Analytical methods for geochemical monitoring of CCS sites 13

Table A2. (continued)

Method detec- Last
Elements Analytical methods Matrix Unit Equipment
tion limit (MDL) reviewed
Mg ISO 7980:1986 Raw, drinking water 0.9–5(a) mg/L Flame AAS 2012
EPA 200.5 Drinking water >IDL – AVICP- OES 2003
EPA 200.7 Water, wastewater >0.02 mg/L ICP-OES 2001
EPA 6010C Any solution >IDL – ICP-OES 2000
EPA 242.1 Water 0.02–0.5(a) mg/L AAS (direct aspiration) 1974
USGS I-4471-97 Whole-water >3 g/L ICP-OES 2003
USGS I-2020-05, Water, biota/sediment/soil digestates >0.009 g/L cICP-MS 2006
I-4020-05
USGS I-1447-85, Water, brine 0.01–50(a) mg/L AAS (direct aspiration) –
I-3447-85
Mn ISO 14911:1998 Drinking, surface, waste water 0.5–50(a) mg/L IC 2014
ISO 11885:2007 Ground, surface, raw, potable, waste water >IDL – ICP-OES 2016
ISO 17294-2:2016 Drinking, surface, groundwater, waste water, >3 g/L ICP-MS 2016
eluates
ISO 6333:1986 Surface, drinking water 0.01–5(a) mg/L Spectrometer 2012
EPA 200.5 Drinking water >0.06 g/L AVICP- OES 2003
EPA 200.7 Water, wastewater >0.001 mg/L ICP-OES 2001
EPA 6010C Any solution >IDL – ICP-OES 2000
EPA 200.8 Ground, surface, drinking, wastewater, >0.02 g/L ICP-MS 1994
sludge, soil
EPA 200.9 Ground, surface, drinking water, storm run- >0.3 g/L AAS (graphite furnace) 1994
off, industrial/domestic wastewater, sedi-
ment, sludge, soil
EPA 243.1 Water 0.1–3(a) mg/L AAS (direct aspiration) 1978
EPA 243.2 Water 1–30(a) g/L AAS (furnace technique) 1978
USGS I-4471-97 Whole-water >2 g/L ICP-OES, ICP-MS 2003
>0.06
USGS I-1454-85, Water 10–1,000(a) g/L AAS (direct aspiration) –
I-3454-85
USGS I-1455-85 Low ionic-strength water 0.2–12(a) g/L AAS (graphite furnace) –
USGS I-1456-85 Water, brine 1–100(a) g/L AAS (direct aspiration) –
Na ISO 14911:1998 Drinking, surface, waste water 0.1–10(a) mg/L IC 2014
ISO 11885:2007 Ground, surface, raw, potable, waste water >IDL – ICP-OES 2016
ISO 17294-2:2016 Drinking, surface, groundwater, waste water, >10 g/L ICP-MS 2016
eluates
EPA 200.5 Drinking water >IDL – AVICP- OES 2003
EPA 200.7 Water, wastewater >0.03 mg/L ICP- OES 2001
EPA 273.1 Water 0.03–1(a) mg/L AAS (direct aspiration) –
EPA 6010C Any solution >IDL – ICP- OES 2000
USGS I-4471-97 Whole-water >70 g/L ICP-OES 2003
USGS I-2020-05, Water, biota/sediment/soil digestates >0.09 mg/L cICP-MS 2006
I-4020-05
USGS I-1735-85, Water, brine 0.01–80(a) mg/L AAS (direct aspiration) –
I-3735-85
USGS I-3736-85 Ambient water, domestic/industrial effluent 0.1–80(a) mg/L AAS (direct aspiration) –
Si/SiO2 ISO 11885:2007 Ground, surface, raw, potable, waste water >IDL – ICP-OES 2016
EPA 200.5 Drinking water >IDL μg/L AVICP-OES 2003
EPA 200.7 Water, wastewater >0.02 mg/L ICP-OES 2001
EPA 6010C Any solution >IDL – ICP-OES 2000
USGS I-4471-97 Whole-water >70 μg/L ICP-OES 2003
USGS I-2020-05, Water, biota/sediment/soil digestates >0.03 mg/L cICP-MS 2006
I-4020-05
(a)
Optimum concentration range.

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