A study by the University of Iowa researchers, titled "Understanding the Radioactive Ingrowth and Decay of Naturally Occurring Radioactive Materials in the Environment: An Analysis of Produced Fluids from the Marcellus Shale" and published in the peer reviewed journal Environmental Health Perspectives in April 2015. The research reportedly shows a new method for testing the total potential radioactivity of shale wastewater not previously considered. The chief shortcoming of the research is that it is based on a single sample from a single Marcellus Shale well.
Separation, characterization and leaching behaviors of heavy metals in contam...Alexander Decker
This document discusses a study on the separation, characterization, and leaching behaviors of heavy metals in contaminated river sediments. The study involved analyzing sediment samples from rivers in central Taiwan to understand the concentration and chemical forms of heavy metals present, including copper, lead, zinc, nickel, and chromium. Sequential extraction tests showed most metals exceeded sediment quality standards. Acid washing experiments found heavy metal removal efficiencies were highest for nickel, zinc, lead, copper, and chromium when washed with HCl for 120 minutes. Results indicate some metals exist in residual forms in sediments but become more exchangeable after washing, increasing bioavailability.
This document summarizes a study that surveyed the concentration of nitrates in drinking water distribution systems in Kashan County, Iran. Water samples were taken from 25 sampling points in Kashan and 6 surrounding towns. The average nitrate concentration was found to be 17.5 mg/L, with a maximum of 27.4 mg/L and minimum of 9.5 mg/L. 68% of samples had nitrate concentrations below 20 mg/L, which is considered slightly contaminated, while 32% were between 20-45 mg/L, considered contaminated. No samples exceeded the WHO guideline of 45 mg/L. However, nitrate levels have been increasing over the past decade and continued agricultural and industrial activity could further drive up
This document is the curriculum vitae of Court D. Sandau, which provides information about his education, career experience, areas of expertise, and selected project experiences. It outlines that Dr. Sandau has a PhD in Chemistry and is the principal and senior chemist at Chemistry Matters, with over 20 years of experience in environmental forensics, expert witness work, and scientific investigations. It also provides details on 3 litigation support projects involving chemical fingerprinting to determine the source of environmental contamination.
Univ of Iowa Research on Best Methods to Detect Radioactivity in Marcellus Sh...Marcellus Drilling News
The document discusses methods for determining radium levels in hydraulic fracturing flowback water from Marcellus Shale. It tested several common radium analysis methods using a representative Marcellus Shale flowback water sample, including:
1) Wet chemical approaches like EPA method 903.0 (BaSO4 coprecipitation) recovered as little as 1% of radium, questioning the reliability of these techniques for high ionic strength flowback water.
2) Nondestructive techniques like radon emanation measurement and high-purity germanium gamma spectroscopy were effective in determining radium levels.
3) The results suggest that nondestructive spectroscopic techniques are most appropriate for analysis of radium in
John F. Schneider is the Group Leader of the Chemical Analysis and Research Group at Argonne National Laboratory. He has over 30 years of experience in analytical chemistry, developing methods for the analysis of chemicals including chemical warfare agents, explosives, and toxins. He currently manages several projects involving chemical detection and analysis to support national security and medical research.
Daniel K. Lesniewski has over 15 years of experience in organic synthesis, analytical chemistry, and process development. He holds an M.Sc. in Organic Chemistry from Colorado State University-Pueblo and a B.Sc. in Chemistry from the same institution. His experience includes positions at Corden Pharma, Avista Pharma Solutions, General Air, Amgen, Lexmark International, and Colorado State University, where he has experience in multi-step organic synthesis, analytical instrumentation, scale-up reactions, method development, and research.
This document analyzes heavy metal concentrations in water samples collected from Singanamala Tank in Andhra Pradesh, India between 2011-2013. Heavy metals measured include lithium, aluminum, vanadium, iron, cobalt, nickel, copper, zinc, arsenic, silver, cadmium, cesium, barium, titanium, lead, and uranium. Testing was done using inductively coupled plasma-mass spectrometry. Results found that concentrations of most metals exceeded desirable limits for drinking water set by Indian standards. The high levels were attributed to agricultural, industrial, and domestic waste entering the water body. In conclusion, the tank water was contaminated and could harm animal and human health if consumed.
SEDIMENT QUALITY ASSESSMENT OF AVARAGERE LAKE, DAVANAGERE CITY - A CASE STUDYAM Publications
Avaragere Lake in Davangere was studied for chemical and physical parameters at five locations, for a period of six months (April 2014 to Sep 2014). Lake has been subjected to human interferences regularly and water quality was to be getting deteriorated profoundly. Major anthropogenic activities practiced in and around the stretch: agriculture, discharging of sewage waste etc was generating serious threat to the biota of the lake by altering the physical, chemical and biological concentration of the lake system. The other possibility is that since there are no major industries in the project area, the major source of organic pollutants is only the domestic source.
Monthly data’s been collected. Different parameters studied were pH, Conductivity, organic carbon, nitrogen, phosphorus, potassium, zinc, copper, iron, organothiophosphate and pyrethroid content. The results obtained from the above study indicate that the water of Avaragere Lake organothiophosphate and pyrethroid content shows very low concentrations even at nanogram. Manganese and iron concentrations of sediment sample in avaragere lake shows high level of pollution and ecological balance of Lake is totally disturbed.
Separation, characterization and leaching behaviors of heavy metals in contam...Alexander Decker
This document discusses a study on the separation, characterization, and leaching behaviors of heavy metals in contaminated river sediments. The study involved analyzing sediment samples from rivers in central Taiwan to understand the concentration and chemical forms of heavy metals present, including copper, lead, zinc, nickel, and chromium. Sequential extraction tests showed most metals exceeded sediment quality standards. Acid washing experiments found heavy metal removal efficiencies were highest for nickel, zinc, lead, copper, and chromium when washed with HCl for 120 minutes. Results indicate some metals exist in residual forms in sediments but become more exchangeable after washing, increasing bioavailability.
This document summarizes a study that surveyed the concentration of nitrates in drinking water distribution systems in Kashan County, Iran. Water samples were taken from 25 sampling points in Kashan and 6 surrounding towns. The average nitrate concentration was found to be 17.5 mg/L, with a maximum of 27.4 mg/L and minimum of 9.5 mg/L. 68% of samples had nitrate concentrations below 20 mg/L, which is considered slightly contaminated, while 32% were between 20-45 mg/L, considered contaminated. No samples exceeded the WHO guideline of 45 mg/L. However, nitrate levels have been increasing over the past decade and continued agricultural and industrial activity could further drive up
This document is the curriculum vitae of Court D. Sandau, which provides information about his education, career experience, areas of expertise, and selected project experiences. It outlines that Dr. Sandau has a PhD in Chemistry and is the principal and senior chemist at Chemistry Matters, with over 20 years of experience in environmental forensics, expert witness work, and scientific investigations. It also provides details on 3 litigation support projects involving chemical fingerprinting to determine the source of environmental contamination.
Univ of Iowa Research on Best Methods to Detect Radioactivity in Marcellus Sh...Marcellus Drilling News
The document discusses methods for determining radium levels in hydraulic fracturing flowback water from Marcellus Shale. It tested several common radium analysis methods using a representative Marcellus Shale flowback water sample, including:
1) Wet chemical approaches like EPA method 903.0 (BaSO4 coprecipitation) recovered as little as 1% of radium, questioning the reliability of these techniques for high ionic strength flowback water.
2) Nondestructive techniques like radon emanation measurement and high-purity germanium gamma spectroscopy were effective in determining radium levels.
3) The results suggest that nondestructive spectroscopic techniques are most appropriate for analysis of radium in
John F. Schneider is the Group Leader of the Chemical Analysis and Research Group at Argonne National Laboratory. He has over 30 years of experience in analytical chemistry, developing methods for the analysis of chemicals including chemical warfare agents, explosives, and toxins. He currently manages several projects involving chemical detection and analysis to support national security and medical research.
Daniel K. Lesniewski has over 15 years of experience in organic synthesis, analytical chemistry, and process development. He holds an M.Sc. in Organic Chemistry from Colorado State University-Pueblo and a B.Sc. in Chemistry from the same institution. His experience includes positions at Corden Pharma, Avista Pharma Solutions, General Air, Amgen, Lexmark International, and Colorado State University, where he has experience in multi-step organic synthesis, analytical instrumentation, scale-up reactions, method development, and research.
This document analyzes heavy metal concentrations in water samples collected from Singanamala Tank in Andhra Pradesh, India between 2011-2013. Heavy metals measured include lithium, aluminum, vanadium, iron, cobalt, nickel, copper, zinc, arsenic, silver, cadmium, cesium, barium, titanium, lead, and uranium. Testing was done using inductively coupled plasma-mass spectrometry. Results found that concentrations of most metals exceeded desirable limits for drinking water set by Indian standards. The high levels were attributed to agricultural, industrial, and domestic waste entering the water body. In conclusion, the tank water was contaminated and could harm animal and human health if consumed.
SEDIMENT QUALITY ASSESSMENT OF AVARAGERE LAKE, DAVANAGERE CITY - A CASE STUDYAM Publications
Avaragere Lake in Davangere was studied for chemical and physical parameters at five locations, for a period of six months (April 2014 to Sep 2014). Lake has been subjected to human interferences regularly and water quality was to be getting deteriorated profoundly. Major anthropogenic activities practiced in and around the stretch: agriculture, discharging of sewage waste etc was generating serious threat to the biota of the lake by altering the physical, chemical and biological concentration of the lake system. The other possibility is that since there are no major industries in the project area, the major source of organic pollutants is only the domestic source.
Monthly data’s been collected. Different parameters studied were pH, Conductivity, organic carbon, nitrogen, phosphorus, potassium, zinc, copper, iron, organothiophosphate and pyrethroid content. The results obtained from the above study indicate that the water of Avaragere Lake organothiophosphate and pyrethroid content shows very low concentrations even at nanogram. Manganese and iron concentrations of sediment sample in avaragere lake shows high level of pollution and ecological balance of Lake is totally disturbed.
Analysis the amounts of heavy metals and trace elements in water of different...VikashKKushwaha
The study was aimed to analyze the concentration of metals including heavy metals and trace elements in the water of four different small water bodies or sources including two pond, one lake and one river around Ranchi city. The metals or trace elements such as Ag, Al, B, Bi, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb and Zn were analyzed by using Inductively Coupled Plasma- Optical Emission Spectroscopy technique. The results indicated that the concentration of approximately all the metals, heavy metals, and trace elements in these water bodies was found within the maximum permissible limit set by IS:2296, EPA, and WHO for surface water quality standards. Higher concentrations of Al in Lake of Chamber, Bi, and Mn in Jumar river than other sites were reported.
This document discusses the complexities in monitoring and characterizing airborne particulate matter (PM). It notes that PM classifications, analysis techniques, and chemical compositions can vary significantly between locations and sources. Advances in monitoring now allow analysis of finer PM fractions as well as physical, chemical, and biological particle properties. However, this additional data reveals new challenges for standards development. The document also outlines gaps in current understanding around secondary PM formation, indoor/outdoor sources, and background concentrations. New monitoring techniques like open-path spectroscopy are providing more detailed real-time air quality data over larger areas. Overall, characterizing PM remains an important but complex area of research.
New type of multi-purpose standard radon chamber in south koreaAlexander Decker
This document summarizes the development of a new multi-purpose standard radon chamber in South Korea. The chamber was designed to evaluate radon emission rates from natural and artificial sources under different conditions, calibrate radon detectors, and assess the efficiency of radon mitigation systems. It has the ability to control temperature, humidity and air flow. Computational fluid dynamics modeling can also simulate radon movement within the chamber. The chamber fills an important need as existing chambers in South Korea are not widely used due to lack of demand. It will help advance radon research and regulation in the country.
Final Report Daad13 02 C 0015 Part5 App A Finscore
1) The document presents surface-enhanced Raman spectroscopy (SERS) as a potential technique for rapid identification of chemical warfare agents and related compounds.
2) Preliminary SERS measurements are shown for the nerve agent simulant dimethyl methylphosphonate and the mustard gas simulant 2-chloroethyl ethyl sulfide, demonstrating molecular fingerprinting capabilities.
3) SERS is also applied to measurement of chemical agent hydrolysis products such as pinacolyl methylphosphonate and methylphosphonic acid, showing its ability to analyze breakdown components.
The NEERI Chennai Zonal Laboratory has been conducting environmental research and assisting local industries since 1969. It focuses on areas like pollution monitoring, biotechnology, waste management, and more. The laboratory has contributed significantly to solving pollution problems in southern India and conducted many projects with international organizations. It has provided important wastewater treatment solutions and environmental impact assessments for major projects.
The document discusses membrane bioreactor (MBR) systems for wastewater treatment. It provides common ranges for key design parameters like membrane flux rates, mixed liquor suspended solids concentrations, and aeration requirements. The text indicates MBR systems require careful design to prevent fouling and ensure integrity. It also notes TCEQ may require a pilot study or 2-year performance bond for non-standard MBR proposals.
Leachate Monitoring In The Extractive Industry: A Case Study Of Nigerian Liqu...IJERA Editor
Activities of extractive industry (NLNG is typical) introduces some chemical substances into the groundwater.
These change the groundwater signature and bioaccumulation of some of these classified as hazardous may
result in various wealth challenges. Seven areas within the plant where identified by NLNG Six as high risk
pollution areas and one (Nature Park) as no pollution risk area. Groundwater samples were collected from all
seven areas and analyzed for the presence of Cu, Cr, Zn, nitrate, phosphate and PH. Samples from the no
pollution risk area served as control. Results were compared with WHO limits. Except for Cr content which was
stable, other results showed fluctuations with time, albeit on the increase, though all remained within WHO
limits. Nitrate value is fast approaching limit and requires urgent attention. Unexpected high values of the
measured parameters were observed at Nature Park (no pollution risk area) even beyond the high risk pollution
areas. This precludes NLNG activities being responsible. The necessity of pre-activity groundwater quality
assessment is thus established. Close monitoring of groundwater quality of the extractive industry zones is vital
for the protection of source quality.
Artificial Neural Network for Modeling Nitrate Pollution of GroundwaterKaveh Ostad-Ali-Askari
This document presents a study that used an artificial neural network (ANN) to model and estimate nitrate pollution in groundwater in the marginal area of the Zayandeh-rood River in Isfahan, Iran. 100 wells in the area were sampled for water quality parameters including nitrate concentration. A three-layer perceptron neural network with one hidden layer and 19 neurons was developed using MATLAB software. The network was trained using the backpropagation learning algorithm and sigmoid activation function. The ANN model was able to accurately model nitrate concentrations in the groundwater and can be applied to investigate water quality parameters.
This document summarizes the environmental effects monitoring program conducted during the remediation of one of Canada's most polluted sites in Sydney Harbour. The monitoring program included water quality sampling, sediment quality sampling, mussel tissue sampling, crab tissue sampling, and benthic community assessments. The results showed that most contaminant levels did not significantly change or decrease over time, consistent with predictions that remediation would not cause significant negative environmental impacts. Some lessons learned included issues with non-detect values and challenges conducting the monitoring program during large dredging activities.
Determinar la toxicitat dels sediments en els ecosistemes aquàtics és un repte, i és necessari per a una adequada avaluació del risc toxicològic en aquests ecosistemes. En les darreres dècades s’han estudiat i aplicat diferents eines (ex. tests de laboratori amb diferents concentracions, tests amb l’aigua intersticial, estudis de bioacumulació, índexs de toxicitat). Actualment es recomana l'aplicació conjunta d'eines químiques, ecològiques i toxicològiques per a una adequada avaluació. En aquest treball utilitzem l’aproximació de les Toxic Units, tests de toxicitat amb l’aigua intersticial (Vibrio fischeri, Pseudokirchneriella subcapitata i Daphnia magna) i tests d'exposició amb el sediment (V. fischeri, Chironomus riparius), juntament amb l’estudi de la comunitat d'invertebrats, per detectar respostes a curt i llarg termini en quatre rius de la Península Ibèrica: el Llobregat, l’Ebre, el Xúquer i el Guadalquivir.
by Núria de Castro-Català, Maja Kuzmanovic, Neus Roig, Jordi Sierra, Antoni Ginebreda, Damià Barceló, Sandra Pérez, Mira Petrovic, Yolanda Picó, Marta Schumacher and Isabel Muñoz
Assessment of Physico-Chemical Properties and Toxic Heavy Metals in Water Fro...IRJET Journal
The document analyzes water quality samples from three sites along the Kali River in Meerut, India. Physicochemical parameters like pH, TDS, conductivity, BOD, COD and heavy metals were found to exceed permissible limits for drinking water. pH ranged from 7.1 to 8.3, TDS from 1643-3145 mg/L, and BOD and COD indicated high organic pollution. Dissolved oxygen levels were very low. Heavy metal analysis found levels of Pb, Cr, Cd, Hg, Cu, Ni, Mn, Fe and Zn exceeded limits for irrigation and drinking water. The study indicates the river water is polluted from industrial and domestic waste and requires treatment before use.
1) Silver nanoparticles are intentionally produced engineered nanomaterials that are being used in many consumer products due to their antibacterial properties. However, there is concern about their potential impacts on human health and the environment.
2) The project aimed to develop methods to detect silver nanoparticles in water, determine their toxicological effects in aquatic environments, and develop risk assessment protocols.
3) Key findings included that activated charcoal can effectively capture silver nanoparticles from water, effects were observed on aquatic organisms in toxicity tests, and current models estimate low environmental concentrations pose low risks to human health through drinking water. However, more studies are needed to monitor silver nanoparticles in Ireland's environment and risks.
LGC is addressing the UK's chemical and bio-measurement needs to support key industries like healthcare, food, and energy. LGC researchers are developing new methods to accurately measure pollutants like PBDEs in water samples to help enforce the EU Water Framework Directive and clean up rivers and lakes. They are also studying microbial communities as bioindicators of water quality to rapidly assess the impacts of pollution and help mitigate threats to water resources.
This document summarizes a study that assessed the ecological impacts of urban runoff from two catchments on receiving aquatic ecosystems using local periphyton communities. Periphyton were colonized for 2 weeks in rivers receiving runoff and in a non-receiving upstream reference site. The receiving communities were evaluated for photosynthetic efficiency and tolerance to copper, identified as a significant runoff stressor. The hypothesis tested was that runoff degrades communities by making them more sensitive to runoff stressors. Results indicated higher copper tolerance than water quality guidelines, showing the value of using local communities for site-specific ecological risk assessment of runoff impacts.
This document describes a study that investigated the bioconcentration of three nitrogen-based compounds (4-nitroanisole, 3,5-dinitro-o-toluamide, and 2-methoxy-5 nitropyridine) in earthworms. Toxicity tests were first conducted to determine sublethal exposure concentrations for earthworms. Then, earthworms were exposed to the compounds in an aqueous medium for up to 14 days to estimate bioconcentration factors. Tissue analysis found rapid uptake of the compounds, with steady state reached within 24 h. Estimated steady-state bioconcentration factors were 47, 6, and 11 for the three compounds, respectively. These results provide new bioconcentration data that
Multidisciplinary Research Week 2013 at the University of Southampton. #MDRWeek. World Water Day and International Year of Water Cooperation 2013.
Water quality: addressing global problems at source’, Presentation by Dr Jim Wright, Geography and Environment, University of Southampton.
See the latest videos, interviews, pictures, tweets and views from the floor at: www.southampton.ac.uk/multidisciplinary
11.application of principal component analysis & multiple regression models i...Alexander Decker
Principal component analysis and multiple regression models were used to analyze water quality data from four sampling points along the Jakara River in Nigeria. PCA identified five factors explaining 83.1% of the variance in water quality: 1) ionic pollution from salts and minerals, 2) erosion runoff affecting suspended solids and turbidity, 3) domestic pollution shown by biochemical oxygen demand and chemical oxygen demand, 4) dilution affecting temperature and dissolved oxygen, and 5) agricultural runoff containing nitrates and phosphates. Multiple regression identified dissolved oxygen, biochemical oxygen demand, suspended solids, total solids, and chloride as best predicting water quality variation, explaining 94.2% of variability.
This document provides an outline for a project to design a water treatment system for agricultural irrigation from a reservoir. The system will treat water from Lake Issaqueena in Clemson, South Carolina to remove algae and disinfect microbes. The objectives are to develop a facility meeting water quality standards without clogging irrigation systems. Approaches include identifying water impurities, research filtration and disinfection methods, and designing a multi-stage treatment system. Deliverables will be water quality standards, treatment designs, and a life cycle analysis. The project addresses the challenges of access to clean water and food security.
Using Fingerprinting Techniques and Multivariate Statistics to Identify Natur...Chemistry Matters Inc.
This document presents the findings of a study using fingerprinting techniques and multivariate statistics to distinguish between natural and anthropogenic salinity in soil samples. Radar plots and statistical analysis of parameters like chloride, calcium, sodium, and sulfate concentrations were used to group 54 site samples. Three distinct fingerprint patterns were identified, with two samples having natural salinity fingerprints similar to background samples, 48 samples having anthropogenic fingerprints different than background, and 3 samples having another separate fingerprint. Spatial analysis found the sample groupings correlated with wellsite features. The techniques were able to distinguish anthropogenic impacts despite low overall salinity levels.
Philippe Tob presented information on water usage for shale gas extraction. He discussed (1) the large quantities of water needed for fracturing shale rock and producing shale gas, (2) the quality of water used and produced water, and (3) potential solutions for treating and reusing water through emerging technologies. He concluded that with sustainable water management solutions available, shale gas exploitation could be a blessing for the water industry through new growth and innovation opportunities.
Analysis the amounts of heavy metals and trace elements in water of different...VikashKKushwaha
The study was aimed to analyze the concentration of metals including heavy metals and trace elements in the water of four different small water bodies or sources including two pond, one lake and one river around Ranchi city. The metals or trace elements such as Ag, Al, B, Bi, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb and Zn were analyzed by using Inductively Coupled Plasma- Optical Emission Spectroscopy technique. The results indicated that the concentration of approximately all the metals, heavy metals, and trace elements in these water bodies was found within the maximum permissible limit set by IS:2296, EPA, and WHO for surface water quality standards. Higher concentrations of Al in Lake of Chamber, Bi, and Mn in Jumar river than other sites were reported.
This document discusses the complexities in monitoring and characterizing airborne particulate matter (PM). It notes that PM classifications, analysis techniques, and chemical compositions can vary significantly between locations and sources. Advances in monitoring now allow analysis of finer PM fractions as well as physical, chemical, and biological particle properties. However, this additional data reveals new challenges for standards development. The document also outlines gaps in current understanding around secondary PM formation, indoor/outdoor sources, and background concentrations. New monitoring techniques like open-path spectroscopy are providing more detailed real-time air quality data over larger areas. Overall, characterizing PM remains an important but complex area of research.
New type of multi-purpose standard radon chamber in south koreaAlexander Decker
This document summarizes the development of a new multi-purpose standard radon chamber in South Korea. The chamber was designed to evaluate radon emission rates from natural and artificial sources under different conditions, calibrate radon detectors, and assess the efficiency of radon mitigation systems. It has the ability to control temperature, humidity and air flow. Computational fluid dynamics modeling can also simulate radon movement within the chamber. The chamber fills an important need as existing chambers in South Korea are not widely used due to lack of demand. It will help advance radon research and regulation in the country.
Final Report Daad13 02 C 0015 Part5 App A Finscore
1) The document presents surface-enhanced Raman spectroscopy (SERS) as a potential technique for rapid identification of chemical warfare agents and related compounds.
2) Preliminary SERS measurements are shown for the nerve agent simulant dimethyl methylphosphonate and the mustard gas simulant 2-chloroethyl ethyl sulfide, demonstrating molecular fingerprinting capabilities.
3) SERS is also applied to measurement of chemical agent hydrolysis products such as pinacolyl methylphosphonate and methylphosphonic acid, showing its ability to analyze breakdown components.
The NEERI Chennai Zonal Laboratory has been conducting environmental research and assisting local industries since 1969. It focuses on areas like pollution monitoring, biotechnology, waste management, and more. The laboratory has contributed significantly to solving pollution problems in southern India and conducted many projects with international organizations. It has provided important wastewater treatment solutions and environmental impact assessments for major projects.
The document discusses membrane bioreactor (MBR) systems for wastewater treatment. It provides common ranges for key design parameters like membrane flux rates, mixed liquor suspended solids concentrations, and aeration requirements. The text indicates MBR systems require careful design to prevent fouling and ensure integrity. It also notes TCEQ may require a pilot study or 2-year performance bond for non-standard MBR proposals.
Leachate Monitoring In The Extractive Industry: A Case Study Of Nigerian Liqu...IJERA Editor
Activities of extractive industry (NLNG is typical) introduces some chemical substances into the groundwater.
These change the groundwater signature and bioaccumulation of some of these classified as hazardous may
result in various wealth challenges. Seven areas within the plant where identified by NLNG Six as high risk
pollution areas and one (Nature Park) as no pollution risk area. Groundwater samples were collected from all
seven areas and analyzed for the presence of Cu, Cr, Zn, nitrate, phosphate and PH. Samples from the no
pollution risk area served as control. Results were compared with WHO limits. Except for Cr content which was
stable, other results showed fluctuations with time, albeit on the increase, though all remained within WHO
limits. Nitrate value is fast approaching limit and requires urgent attention. Unexpected high values of the
measured parameters were observed at Nature Park (no pollution risk area) even beyond the high risk pollution
areas. This precludes NLNG activities being responsible. The necessity of pre-activity groundwater quality
assessment is thus established. Close monitoring of groundwater quality of the extractive industry zones is vital
for the protection of source quality.
Artificial Neural Network for Modeling Nitrate Pollution of GroundwaterKaveh Ostad-Ali-Askari
This document presents a study that used an artificial neural network (ANN) to model and estimate nitrate pollution in groundwater in the marginal area of the Zayandeh-rood River in Isfahan, Iran. 100 wells in the area were sampled for water quality parameters including nitrate concentration. A three-layer perceptron neural network with one hidden layer and 19 neurons was developed using MATLAB software. The network was trained using the backpropagation learning algorithm and sigmoid activation function. The ANN model was able to accurately model nitrate concentrations in the groundwater and can be applied to investigate water quality parameters.
This document summarizes the environmental effects monitoring program conducted during the remediation of one of Canada's most polluted sites in Sydney Harbour. The monitoring program included water quality sampling, sediment quality sampling, mussel tissue sampling, crab tissue sampling, and benthic community assessments. The results showed that most contaminant levels did not significantly change or decrease over time, consistent with predictions that remediation would not cause significant negative environmental impacts. Some lessons learned included issues with non-detect values and challenges conducting the monitoring program during large dredging activities.
Determinar la toxicitat dels sediments en els ecosistemes aquàtics és un repte, i és necessari per a una adequada avaluació del risc toxicològic en aquests ecosistemes. En les darreres dècades s’han estudiat i aplicat diferents eines (ex. tests de laboratori amb diferents concentracions, tests amb l’aigua intersticial, estudis de bioacumulació, índexs de toxicitat). Actualment es recomana l'aplicació conjunta d'eines químiques, ecològiques i toxicològiques per a una adequada avaluació. En aquest treball utilitzem l’aproximació de les Toxic Units, tests de toxicitat amb l’aigua intersticial (Vibrio fischeri, Pseudokirchneriella subcapitata i Daphnia magna) i tests d'exposició amb el sediment (V. fischeri, Chironomus riparius), juntament amb l’estudi de la comunitat d'invertebrats, per detectar respostes a curt i llarg termini en quatre rius de la Península Ibèrica: el Llobregat, l’Ebre, el Xúquer i el Guadalquivir.
by Núria de Castro-Català, Maja Kuzmanovic, Neus Roig, Jordi Sierra, Antoni Ginebreda, Damià Barceló, Sandra Pérez, Mira Petrovic, Yolanda Picó, Marta Schumacher and Isabel Muñoz
Assessment of Physico-Chemical Properties and Toxic Heavy Metals in Water Fro...IRJET Journal
The document analyzes water quality samples from three sites along the Kali River in Meerut, India. Physicochemical parameters like pH, TDS, conductivity, BOD, COD and heavy metals were found to exceed permissible limits for drinking water. pH ranged from 7.1 to 8.3, TDS from 1643-3145 mg/L, and BOD and COD indicated high organic pollution. Dissolved oxygen levels were very low. Heavy metal analysis found levels of Pb, Cr, Cd, Hg, Cu, Ni, Mn, Fe and Zn exceeded limits for irrigation and drinking water. The study indicates the river water is polluted from industrial and domestic waste and requires treatment before use.
1) Silver nanoparticles are intentionally produced engineered nanomaterials that are being used in many consumer products due to their antibacterial properties. However, there is concern about their potential impacts on human health and the environment.
2) The project aimed to develop methods to detect silver nanoparticles in water, determine their toxicological effects in aquatic environments, and develop risk assessment protocols.
3) Key findings included that activated charcoal can effectively capture silver nanoparticles from water, effects were observed on aquatic organisms in toxicity tests, and current models estimate low environmental concentrations pose low risks to human health through drinking water. However, more studies are needed to monitor silver nanoparticles in Ireland's environment and risks.
LGC is addressing the UK's chemical and bio-measurement needs to support key industries like healthcare, food, and energy. LGC researchers are developing new methods to accurately measure pollutants like PBDEs in water samples to help enforce the EU Water Framework Directive and clean up rivers and lakes. They are also studying microbial communities as bioindicators of water quality to rapidly assess the impacts of pollution and help mitigate threats to water resources.
This document summarizes a study that assessed the ecological impacts of urban runoff from two catchments on receiving aquatic ecosystems using local periphyton communities. Periphyton were colonized for 2 weeks in rivers receiving runoff and in a non-receiving upstream reference site. The receiving communities were evaluated for photosynthetic efficiency and tolerance to copper, identified as a significant runoff stressor. The hypothesis tested was that runoff degrades communities by making them more sensitive to runoff stressors. Results indicated higher copper tolerance than water quality guidelines, showing the value of using local communities for site-specific ecological risk assessment of runoff impacts.
This document describes a study that investigated the bioconcentration of three nitrogen-based compounds (4-nitroanisole, 3,5-dinitro-o-toluamide, and 2-methoxy-5 nitropyridine) in earthworms. Toxicity tests were first conducted to determine sublethal exposure concentrations for earthworms. Then, earthworms were exposed to the compounds in an aqueous medium for up to 14 days to estimate bioconcentration factors. Tissue analysis found rapid uptake of the compounds, with steady state reached within 24 h. Estimated steady-state bioconcentration factors were 47, 6, and 11 for the three compounds, respectively. These results provide new bioconcentration data that
Multidisciplinary Research Week 2013 at the University of Southampton. #MDRWeek. World Water Day and International Year of Water Cooperation 2013.
Water quality: addressing global problems at source’, Presentation by Dr Jim Wright, Geography and Environment, University of Southampton.
See the latest videos, interviews, pictures, tweets and views from the floor at: www.southampton.ac.uk/multidisciplinary
11.application of principal component analysis & multiple regression models i...Alexander Decker
Principal component analysis and multiple regression models were used to analyze water quality data from four sampling points along the Jakara River in Nigeria. PCA identified five factors explaining 83.1% of the variance in water quality: 1) ionic pollution from salts and minerals, 2) erosion runoff affecting suspended solids and turbidity, 3) domestic pollution shown by biochemical oxygen demand and chemical oxygen demand, 4) dilution affecting temperature and dissolved oxygen, and 5) agricultural runoff containing nitrates and phosphates. Multiple regression identified dissolved oxygen, biochemical oxygen demand, suspended solids, total solids, and chloride as best predicting water quality variation, explaining 94.2% of variability.
This document provides an outline for a project to design a water treatment system for agricultural irrigation from a reservoir. The system will treat water from Lake Issaqueena in Clemson, South Carolina to remove algae and disinfect microbes. The objectives are to develop a facility meeting water quality standards without clogging irrigation systems. Approaches include identifying water impurities, research filtration and disinfection methods, and designing a multi-stage treatment system. Deliverables will be water quality standards, treatment designs, and a life cycle analysis. The project addresses the challenges of access to clean water and food security.
Using Fingerprinting Techniques and Multivariate Statistics to Identify Natur...Chemistry Matters Inc.
This document presents the findings of a study using fingerprinting techniques and multivariate statistics to distinguish between natural and anthropogenic salinity in soil samples. Radar plots and statistical analysis of parameters like chloride, calcium, sodium, and sulfate concentrations were used to group 54 site samples. Three distinct fingerprint patterns were identified, with two samples having natural salinity fingerprints similar to background samples, 48 samples having anthropogenic fingerprints different than background, and 3 samples having another separate fingerprint. Spatial analysis found the sample groupings correlated with wellsite features. The techniques were able to distinguish anthropogenic impacts despite low overall salinity levels.
Philippe Tob presented information on water usage for shale gas extraction. He discussed (1) the large quantities of water needed for fracturing shale rock and producing shale gas, (2) the quality of water used and produced water, and (3) potential solutions for treating and reusing water through emerging technologies. He concluded that with sustainable water management solutions available, shale gas exploitation could be a blessing for the water industry through new growth and innovation opportunities.
A report released May 9, 2012 by the National Resources Defense Council critical of the current methods of handling wastewater that results from hydraulic fracturing of natural gas wells in Pennsylvania. The report details the problems (as they see them), and recommended solutions, which include stricter government controls.
This document discusses water production from shale oil and gas wells. It outlines the characteristics of wastewater at different stages of production. Large volumes of wastewater are produced, including frac flowback water within 30 days, transition water from 31-163 days, and produced water after 164 days. Models are presented to predict water production volumes in different basins based on stage count and other factors. Sources of variability are also examined, such as recycled versus non-recycled water. A water production prediction tool is proposed to estimate volumes.
Sensing for Sustainability: Disaggregated Sensing of Electricity, Gas, and WaterEric Larson
This document summarizes research on disaggregated sensing of water, electricity, and natural gas usage presented by Eric Larson, a PhD candidate at the University of Washington. It describes work on developing low-cost sensing systems called ElectriSense, GasSense and HydroSense to monitor appliance-level usage. Evaluation of ElectriSense in homes showed it could identify electrical events like lamps and laptops turning on with 95% accuracy. GasSense used microphones to detect natural gas events like regulators hissing with similar accuracy. HydroSense monitored home water pressure and usage.
Report: Shale Gas Wastewater Treatment and Disposal in Pennsylvania 2014Marcellus Drilling News
A report issued in August 2015 titled "Shale Gas Development - Summary of Shale Gas Wastewater Treatment and Disposal In Pennsylvania 2014". The report finds drillers in PA produced about 1.8 billion gallons of gas and oil wastewater in 2014--a figure largely unchanged since 2011. The study also finds the shale industry in PA is recycling 91% of the wastewater it produces.
A study published by the U.S. Geological Survey titled "Radium Content of Oil- and Gas-Field Produced Waters in the Northern Appalachian Basin (USA): Summary and Discussion of Data." The study looks at samples from various natural gas and oil wells in Pennsyvlania and New York to determine whether or not there is a higher level of radioactivity in Marcellus Shale wastewater than is found in wastewater from other shale basins.
SlideShare now has a player specifically designed for infographics. Upload your infographics now and see them take off! Need advice on creating infographics? This presentation includes tips for producing stand-out infographics. Read more about the new SlideShare infographics player here: http://wp.me/p24NNG-2ay
This infographic was designed by Column Five: http://columnfivemedia.com/
This document provides tips to avoid common mistakes in PowerPoint presentation design. It identifies the top 5 mistakes as including putting too much information on slides, not using enough visuals, using poor quality or unreadable visuals, having messy slides with poor spacing and alignment, and not properly preparing and practicing the presentation. The document encourages presenters to use fewer words per slide, high quality images and charts, consistent formatting, and to spend significant time crafting an engaging narrative and rehearsing their presentation. It emphasizes that an attractive design is not as important as being an effective storyteller.
No need to wonder how the best on SlideShare do it. The Masters of SlideShare provides storytelling, design, customization and promotion tips from 13 experts of the form. Learn what it takes to master this type of content marketing yourself.
This document provides tips for getting more engagement from content published on SlideShare. It recommends beginning with a clear content marketing strategy that identifies target audiences. Content should be optimized for SlideShare by using compelling visuals, headlines, and calls to action. Analytics and search engine optimization techniques can help increase views and shares. SlideShare features like lead generation and access settings help maximize results.
10 Ways to Win at SlideShare SEO & Presentation OptimizationOneupweb
Thank you, SlideShare, for teaching us that PowerPoint presentations don't have to be a total bore. But in order to tap SlideShare's 60 million global users, you must optimize. Here are 10 quick tips to make your next presentation highly engaging, shareable and well worth the effort.
For more content marketing tips: http://www.oneupweb.com/blog/
How to Make Awesome SlideShares: Tips & TricksSlideShare
Turbocharge your online presence with SlideShare. We provide the best tips and tricks for succeeding on SlideShare. Get ideas for what to upload, tips for designing your deck and more.
New "research" by anti-drilling researchers at Johns Hopkins University that purports to show a connection between fracked shale wells in PA and an increase in radon in PA homes. Johns Hopkins Bloomberg School of Public Health researchers rather simplistically say that levels of radon in PA homes have been going up since 2004--when the first Marcellus Shale well was drilled in the state. They also say prior to 2004 levels of radon in PA homes was pretty much steady-state--that it did not increase. Since the "big thing" that's happened over the past decade is a lot of Marcellus drilling, voila, must be those nasty frackers are the source.
This study analyzed 20 public drinking water wells on Cape Cod, Massachusetts for 92 organic wastewater compounds (OWCs) including pharmaceuticals, hormones, and consumer product chemicals. The goals were to evaluate the presence of OWCs in the wells and determine if surrogates of wastewater impact like nitrate, boron, and residential development could identify wells most impacted by OWCs. Fifteen of the 20 wells contained at least one OWC, with the two most frequently detected being the antibiotic sulfamethoxazole and the perfluorosurfactant perfluorooctane sulfonate. Maximum concentrations of two pharmaceuticals matched or exceeded levels reported in other U.S. public water sources, indicating
This document is a thesis submitted to Plymouth University that examines the statistical reliability of sediment sampling methodology for contaminated estuaries. It analyzes metal concentration data from samples collected on grids from two estuaries in southwest England. Various sampling design elements are evaluated, including sieving pretreatment and spatial variability. Monte Carlo resampling is used to compare three sampling strategies with different sample sizes and spatial scales. The study aims to address assumptions in typical sampling designs and propose a generalized approach grounded in statistical reliability for future contamination surveys.
Nuclear Track Detection of Radon Activities among Branded Bottled Water and L...Premier Publishers
In this study, radon activities and exhalation rate were calculated in ten bottled waters (branded and locally). The measurements were performed by nuclear track detectors. The findings of the study indicated that radon activities in all the analysed samples of branded bottled waters were found to be lower than the maximum contamination level recommended for drinking water by United State Public Health Service (USEPA) and World Health Organization (WHO) guidelines value. Further, the result showed that the mean value of radon activity in local bottled waters is higher than the mean value from branded bottled waters. The results revealed that revealed that all investigated samples of branded bottled water are safe for consumption in Afghanistan from the point of radon activity.
This document presents the results of a study that used mobile mass spectrometry to measure ambient concentrations of benzene, toluene, and xylene compounds (BTEX) near unconventional oil and gas extraction sites in the Eagle Ford Shale region of Texas. The study found highly variable BTEX contamination events originating from specific sources on well pad sites, including natural gas flaring units, condensate tanks, compressor units, and hydrogen sulfide scavengers. Individual wellheads did not contribute significantly to BTEX levels. The detection of point sources indicates that mechanical inefficiencies, rather than the extraction process as a whole, are responsible for releasing these compounds into the air.
1. Three wastewater samples from unconventional drilling operations in West Texas were analyzed using various analytical techniques including GC-MS, ICP-OES, HPLC-HRMS, IC, and tests for TOC/TN, conductivity, and pH.
2. Several compounds known to be components of hydraulic fracturing fluid were detected in two of the wastewater samples, including 2-butoxyethanol, alkyl amines, and cocamide diethanolamines, toluene, and o-xylene.
3. Proper management of the large volumes of wastewater generated from unconventional drilling operations will be important due to both the quantity and variable quality of the wastew
Trace metals concentration determination in domestic waterAlexander Decker
This document analyzes trace metal concentrations in domestic water samples from Keana mine area in Nasarawa State, Nigeria. Water samples were collected from wells, boreholes, and streams in the area and analyzed for concentrations of arsenic, cadmium, chromium, strontium, lead, thorium, and zinc using inductively coupled plasma optical emission spectrometry. The results found high levels of arsenic exceeding WHO guidelines in all samples. Strontium levels were close to the acceptable range. Lead and zinc concentrations were low. The high arsenic levels pose a health risk and suggest closer monitoring of water sources is needed to reduce risks to local inhabitants.
I created this poster for the 2017 Arctic Change Conference.
The poster is a preliminary research that focuses on the Geochemistry of parts of the Canadian Hudson Bay.
Keywords:
Hydrocarbons
Radioisotopes
Redox Elements
Total Organic Carbon
Principal Components Analysis
Sediments
Separation, characterization and leaching behaviors of heavy metals in contam...Alexander Decker
The document summarizes a study on the characterization and leaching behaviors of heavy metals in contaminated river sediments. Sequential extraction tests found that heavy metal concentrations exceeded sediment quality standards. Acidic washing and chelation extraction treatments were then tested to remove heavy metals. Acid washing with 2N HCl for 120 minutes achieved the highest removal rates of 70-90% for different heavy metals. Chelation extraction with 0.5M citric acid for 120 minutes removed 36.69% of copper, while 0.5M EDTA for 120 minutes removed 45.83% of lead and 0.5M malic acid for 120 minutes removed 62.1% of zinc. The study concludes that acid washing and chelation agent extraction
This document presents the results of a systematic study measuring indoor radon concentration levels across the main urban areas of Cyprus. Between 2004-2012, over 400 measurements were taken using portable detectors in the districts of Lefkosia, Lemesos, Larnaka, and Pafos, which are home to 67.3% of Cyprus' population. The districts were divided into 189 grid cells of 1 km2 each. Grid cell mean radon concentrations ranged from 1.7 to 86.4 Bq/m3, with an overall mean of 14.3 Bq/m3. This is lower than the estimated global average of 39 Bq/m3. Equivalent annual effective dose rates were also calculated and
This document summarizes Mark Cohen's presentation on atmospheric mercury modeling at NOAA's Air Resources Laboratory. It discusses accomplishments in trajectory-based and comprehensive atmospheric modeling of mercury using the HYSPLIT-Hg model. The modeling reasonably agrees with wet deposition and atmospheric concentration measurements. It also provides source attribution estimates showing both global and domestic sources contribute to mercury deposition in regions like the Great Lakes. The work supports national and international policy goals on understanding and regulating mercury pollution and its impacts.
TNC REPORT - Modeling nitrogen source loads on the north shore of LI 03-01-2016Gillian Mollod
This document summarizes the results of modeling nitrogen source loads to 13 subwatersheds along the north shore of Long Island from Little Neck Bay to Northport Bay. Wastewater from on-site waste disposal systems like septic tanks and cesspools was found to be the largest source of nitrogen in most subwatersheds. Atmospheric deposition and fertilizer use also contribute nitrogen, but to a lesser degree. The total nitrogen load and appropriate reduction strategies vary between subwatersheds based on their characteristics, and tailored approaches are needed. The modeling incorporated spatial data on land use, population, sewage systems and atmospheric deposition rates to quantify nitrogen inputs from wastewater, fertilizer and air pollution.
This document presents a rapid radiochemical method for analyzing americium-241 in water samples following a homeland security event. The method uses separation techniques to detect americium-241 concentrations on the order of the Safe Drinking Water Act methods, but is not approved for regulatory compliance. It is designed to analyze samples where contamination origins are known or unknown. The method can achieve a required uncertainty of 1.9 picocuries per liter for americium-241 at an analytical action level of 15 picocuries per liter to meet measurement quality objectives for emergency response analysis.
This study analyzed 50 drinking water samples from Erbil City, Iraq for radioactive and chemical contamination. A radiation detector was used to measure levels of U-238, Ra-226, Cs-137, and Sr-90 radionuclides. The results showed low levels of all radionuclides that did not exceed safety standards. Chemical tests found normal levels of parameters like pH, conductivity, chlorine, sodium, magnesium and calcium. Some wells near industrial areas had slightly higher nitrate levels. Overall, the study concluded that radioactivity and chemicals in the city's drinking water do not pose health concerns.
COMPARATIVE STUDY ON HEAVY METAL CHARACTERISTICS OF LEACHATE FROM MUNICIPAL ...IJSIT Editor
Rapid urbanization and population growth are largely responsible for very high increasing rate of
solid waste in the urban areas, its proper management and recycling is major problems of Municipal
Corporation. The analytical analysis revealed that the leachate show high concentration of heavy metals viz.,
Pb, Zn, Fe, Mn and Cu. However, their high concentration in municipal solid waste leachate may cause
contaminants for environmental pollution. Therefore, present investigation deals with analyze the heavy
metals concentration in municipal solid waste leachate.
Assessment Of Heavy Metal In Sediment Of Orogodo River, Agbor, Delta State.docxResearchWap
This study was carried out to examine heavy metals concentration in sediment of upstream and downstream of the entry of the sewage to the Orogodo River, Agbor, Delta state Nigeria . Samples were collected from upstream and downstream and were analyzed for Heavy metals (Cd, Cr, Cu, Fe, Pb, Ni, Ca, Mg, Co, Mn and Zn) by atomic absorption spectrophotometer. It shows the concentration of iron, cadmium, manganese, cobalt, chromium, zinc, magnesium, calcium, nickel, lead and copper in mg/kg in sediments sampled.Some specific physico-chemical characteristics, such as TDS, pH, Temperature and conductivity which are known to influence the interactions and dynamics of metals within the sediment. The mean value of the metals listed above in all the six locations gave 126.09mg/kg, 0.000mg/kg, 0.538mg/kg, 0.000mg/kg, 0.141mg/kg, 1.789mg/kg, 1.258mg/kg, 9.49mg/kg, 0.000mg/kg, 0.112mg/kg and 0.0827mg/kg respectively.. The result of the analysis It shown that the concentrations of heavy metal like Zn, Pb, Cr, Ca, Cu, Co, Mg, Mn, Cd and Ni in the sediment are low, but require monitoring to prevent an increase. Hence the concentration of Fe is higher when compared with the WHO and FEPA standard for sediment which may constitute risk to the environment. The concentration of heavy metals varies for the different locations. Based on the result of the analysis, recommendations were offered to reduce the concentration of heavy metal of the river.
The document describes previous models for determining total organic carbon (TOC) content based on well log data that had limitations and inaccuracies. It then discusses the development of a new artificial neural network model to estimate TOC for Barnett and Devonian shale formations using core TOC data and well logs as inputs. The neural network model predicted TOC for Barnett shale with high accuracy, with average absolute deviation of 0.91 wt% and R2 of 0.93 compared to measured TOC. It also outperformed previous models for estimating TOC in Devonian shale, achieving an average absolute deviation of 0.99 wt% and R2 of 0.89.
This study aims to analyze the bioaccumulation of iron, cobalt, nickel, and copper in goldfish and determine their toxic effects. Laboratory testing will be conducted to measure metal content in goldfish tissues. The stress responses and toxicity levels caused by metal nanoparticles will be assessed through statistical analysis of histopathological changes and behavior alterations in goldfish. The risk posed to aquatic species, environments, and ecosystems by the presence of these metals will also be estimated. Quantitative surveys of experts and secondary data from past studies will be used to analyze bioaccumulation and toxicity effects on goldfish in the selected study area.
Environmental applications of nanomaterials 1860946623Subodh Sharma
The document discusses nanoparticle metal oxides and their potential applications for remediating chlorocarbons and organophosphonates. It begins by providing background on the development of nanotechnology and nanomaterials over the past several decades. It then presents an example TEM image of aerogel-prepared nanocrystalline MgO to illustrate how nanoparticle metal oxides have large specific surface areas and fractions of surface atoms available for chemical reactions. Finally, it notes that nanoparticle metal oxides developed by NanoScale Corporation and Kansas State University could be useful for environmental remediation applications due to their chemical reactivity.
Study: Proximity to Natural Gas Wells and Reported Health Status - Results of...Marcellus Drilling News
A "study" published in the online NIH journal Environmental Health Perspectives that supposedly shows there *may be* a link between how close people live to fracked wells and an increase in skin rashes and coughing. However, the authors take pains to make it clear they only have theories--no answers. This is not conclusive in any way, shape or form. The survey relies on self-reporting of health symptoms from only 180 households in a single county in southwestern PA. Small sample, self reported, and funded by anti-drilling organizations. That's all you really need to know.
Similar to Is Marcellus Shale Frack Wastewater More Radioactive Than Previously Thought? (20)
The document summarizes five key facts about the recovery of US shale oil production:
1) Rig counts have increased by 90% since bottoming out in May 2016 and are up 30% year-over-year, signaling increased drilling and production capacity.
2) While decline rates remain steep, production profiles have increased substantially due to technological advances, meaning aggregate supply will be stronger.
3) Preliminary data shows that net new shale supply turned positive in December 2016 for the first time since March 2015, recovering just 7 months after rig counts increased.
4) Increased drilling activity is supported by a large stock of drilled but uncompleted wells, demonstrating the recovery and expansion of the shale sector.
5)
Quarterly legislative action update: Marcellus and Utica shale region (4Q16)Marcellus Drilling News
A quarterly update from the legal beagles at global law firm Norton Rose Fulbright. A quarterly legislative action update for the second quarter of 2016 looking at previously laws acted upon, and new laws introduced, affecting the oil and gas industry in Pennsylvania, Ohio and West Virginia.
An update from Spectra Energy on their proposed $3 billion project to connect four existing pipeline systems to flow more Marcellus/Utica gas to New England. In short, Spectra has put the project on pause until mid-2017 while it attempts to get new customers signed.
A letter from Rover Pipeline to the Federal Energy Regulatory Commission requesting the agency issue the final certificate that will allow Rover to begin tree-clearing and construction of the 511-mile pipeline through Pennsylvania, West Virginia, Ohio and Michigan. If the certificate is delayed beyond the end of 2016, it will delay the project an extra year due to tree-clearing restrictions (to accommodate federally-protected bats).
DOE Order Granting Elba Island LNG Right to Export to Non-FTA CountriesMarcellus Drilling News
An order issued by the U.S. Dept. of Energy that allows the Elba Island LNG export facility to export LNG to countries with no free trade agreement with the U.S. Countries like Japan and India have no FTA with our country (i.e. friendly countries)--so this is good news indeed. Although the facility would have operated by sending LNG to FTA countries, this order opens the market much wider.
A study released in December 2016 by the London School of Economics, titled "On the Comparative Advantage of U.S. Manufacturing: Evidence from the Shale Gas Revolution." While America has enough shale gas to export plenty of it, exporting it is not as economic as exporting oil due to the elaborate processes to liquefy and regassify natural gas--therefore a lot of the gas stays right here at home, making the U.S. one of (if not the) cheapest places on the planet to establish manufacturing plants, especially for manufacturers that use natural gas and NGLs (natural gas liquids). Therefore, manufacturing, especially in the petrochemical sector, is ramping back up in the U.S. For every two jobs created by fracking, another one job is created in the manufacturing sector.
Letter From 24 States Asking Trump & Congress to Withdraw the Unlawful Clean ...Marcellus Drilling News
A letter from the attorneys general from 24 of the states opposed to the Obama Clean Power Plan to President-Elect Trump, RINO Senate Majority Leader Mitch McConnel and RINO House Speaker Paul Ryan. The letter asks Trump to dump the CPP on Day One when he takes office, and asks Congress to adopt legislation to prevent the EPA from such an egregious overreach ever again.
Report: New U.S. Power Costs: by County, with Environmental ExternalitiesMarcellus Drilling News
Natural gas and wind are the lowest-cost technology options for new electricity generation across much of the U.S. when cost, public health impacts and environmental effects are considered. So says this new research paper released by The University of Texas at Austin. Researchers assessed multiple generation technologies including coal, natural gas, solar, wind and nuclear. Their findings are depicted in a series of maps illustrating the cost of each generation technology on a county-by-county basis throughout the U.S.
Annual report issued by the U.S. Energy Information Administration showing oil and natural gas proved reserves, in this case for 2015. These reports are issued almost a year after the period for which they report. This report shows proved reserves for natural gas dropped by 64.5 trillion cubic feet (Tcf), or 16.6%. U.S. crude oil and lease condensate proved reserves also decreased--from 39.9 billion barrels to 35.2 billion barrels (down 11.8%) in 2015. Proved reserves are calculated on a number of factors, including price.
The document is a report from the U.S. Energy Information Administration analyzing oil and gas production from seven regions in the U.S. It includes charts and tables showing historical and projected production levels of oil and gas from each region from 2008 to 2017, as well as metrics like the average production per rig. The regions - Bakken, Eagle Ford, Haynesville, Marcellus, Niobrara, Permian, and Utica - accounted for 92% of domestic oil production growth and all domestic natural gas production growth from 2011-2014.
Velocys is the manufacturer of gas-to-liquids (GTL) plants that convert natural gas (a hyrdocarbon) into other hydrocarbons, like diesel fuel, gasoline, and even waxes. This PowerPoint presentation lays out the Velocys plan to get the company growing. GTL plants have not (so far) taken off in the U.S. Velocys hopes to change that. They specialize in small GTL plants.
PA DEP Revised Permit for Natural Gas Compression Stations, Processing Plants...Marcellus Drilling News
In January 2016, Gov. Wolf announced the DEP would revise its current general permit (GP-5) to update the permitting requirements for sources at natural gas compression, processing, and transmission facilities. This is the revised GP-5.
PA DEP Permit for Unconventional NatGas Well Site Operations and Remote Piggi...Marcellus Drilling News
In January 2016, PA Gov. Wolf announced the Dept. of Environmental Protection would develop a general permit for sources at new or modified unconventional well sites and remote pigging stations (GP-5A). This is the proposed permit.
Onerous new regulations for the Pennsylvania Marcellus Shale industry proposed by the state Dept. of Environmental Protection. The new regs will, according to the DEP, help PA reduce so-called fugitive methane emissions and some types of air pollution (VOCs). This is liberal Gov. Tom Wolf's way of addressing mythical man-made global warming.
The monthly Short-Term Energy Outlook (STEO) from the U.S. Energy Information Administration for December 2016. This issue makes a couple of key points re natural gas: (1) EIA predicts that natural gas production in the U.S. for 2016 will see a healthy decline over 2015 levels--1.3 billion cubic feet per day (Bcf/d) less in 2016. That's the first annual production decline since 2005! (2) The EIA predicts the average price for natural gas at the benchmark Henry Hub will climb from $2.49/Mcf (thousand cubic feet) in 2016 to a whopping $3.27/Mcf in 2017. Why the jump? Growing domestic natural gas consumption, along with higher pipeline exports to Mexico and liquefied natural gas exports.
This document provides an overview of the natural gas market in the Northeast United States, including New England, New York, New Jersey, and Pennsylvania. It details statistics on gas customers, consumption, infrastructure like pipelines and storage, and production. A key point is that the development of the Marcellus Shale in Pennsylvania has significantly increased domestic gas production in the region and reduced its reliance on other supply basins and imports.
The Pennsylvania Public Utility Commission responded to each point raised in a draft copy of the PA Auditor General's audit of how Act 13 impact fee money, raised from Marcellus Shale drillers, gets spent by local municipalities. The PUC says it's not their job to monitor how the money gets spent, only in how much is raised and distributed.
Pennsylvania Public Utility Commission Act 13/Impact Fees Audit by PA Auditor...Marcellus Drilling News
A biased look at how 60% of impact fees raised from PA's shale drilling are spent, by the anti-drilling PA Auditor General. He chose to ignore an audit of 40% of the impact fees, which go to Harrisburg and disappear into the black hole of Harrisburg spending. The Auditor General claims, without basis in fact, that up to 24% of the funds are spent on items not allowed under the Act 13 law.
The final report from the Pennsylvania Dept. of Environmental Protection that finds, after several years of testing, no elevated levels of radiation from acid mine drainage coming from the Clyde Mine, flowing into Ten Mile Creek. Radical anti-drillers tried to smear the Marcellus industry with false claims of illegal wastewater dumping into the mine, with further claims of elevated radiation levels in the creek. After years of testing, the DEP found those allegations to be false.
FERC Order Denying Stay of Kinder Morgan's Broad Run Expansion ProjectMarcellus Drilling News
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El Puerto de Algeciras continúa un año más como el más eficiente del continente europeo y vuelve a situarse en el “top ten” mundial, según el informe The Container Port Performance Index 2023 (CPPI), elaborado por el Banco Mundial y la consultora S&P Global.
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An astonishing, first-of-its-kind, report by the NYT assessing damage in Ukraine. Even if the war ends tomorrow, in many places there will be nothing to go back to.
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Acolyte Episodes review (TV series) The Acolyte. Learn about the influence of the program on the Star Wars world, as well as new characters and story twists.
Is Marcellus Shale Frack Wastewater More Radioactive Than Previously Thought?
1. ENVIRONMENTAL
HEALTH
PERSPECTIVES
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then, please contact ehp508@niehs.nih.gov. Our staff will work with you to
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http://www.ehponline.org
ehp
Understanding the Radioactive Ingrowth and Decay of
Naturally Occurring Radioactive Materials in the
Environment: An Analysis of Produced Fluids from the
Marcellus Shale
Andrew W. Nelson, Eric S. Eitrheim, Andrew W. Knight,
Dustin May, Marinea A. Mehrhoff, Robert Shannon,
Robert Litman, William C. Burnett, Tori Z. Forbes,
and Michael K. Schultz
http://dx.doi.org/10.1289/ehp.1408855
Received: 21 June 2014
Accepted: 11 March 2015
Advance Publication: 2 April 2015
2. 1
Understanding the Radioactive Ingrowth and Decay of Naturally
Occurring Radioactive Materials in the Environment: An Analysis
of Produced Fluids from the Marcellus Shale
Andrew W. Nelson,1,2
Eric S. Eitrheim,3
Andrew W. Knight,3
Dustin May,2
Marinea A.
Mehrhoff,2
Robert Shannon,4
Robert Litman,5
William C. Burnett,6
Tori Z. Forbes,3
and Michael K. Schultz1,7
1
Interdisciplinary Human Toxicology Program, University of Iowa, Iowa City, Iowa, USA;
2
University of Iowa State Hygienic Laboratory, Research Park, Coralville, Iowa, USA;
3
Department of Chemistry, University of Iowa, Iowa City, Iowa, USA; 4
Quality Radioanalytical
Support, Grand Marais, Minnesota, USA; 5
Radiochemistry Laboratory Basics, The Villages,
Florida, USA; 6
Department of Earth, Ocean and Atmospheric Science, Florida State University,
Tallahassee, Florida, USA; 7
Department of Radiology and Department of Radiation Oncology,
Free Radical and Radiation Biology Program, University of Iowa, Iowa City, Iowa, USA
Address correspondence to Michael K. Schultz, Radiology and Radiation Oncology, University
of Iowa, ML B180 FRRB, 500 Newton Road, Iowa City, Iowa 52242 USA. Telephone: +1(319)
335 8017. E-mail: michael-schultz@uiowa.edu
Running title: Radioactivity in shale gas mining waste
Acknowledgments: We kindly acknowledge the staff and faculty at the University of Iowa State
Hygienic Laboratory (SHL) for assisting us in this research. Funding for these experiments was
provided by the U.S. Nuclear Regulatory Commission (NRC-HQ-12-G-38-0041); and
Environmental Management Solutions (Contract EMS FP 07-037-43). R Shannon is employed
3. 2
by Quality Radioanalytical Support, Grand Marais, Minnesota, USA. R Litman is employed by
Radiochemistry Laboratory Basics, The Villages, Florida, USA.
Competing financial interests: MKS is a paid consultant for Speer Law Firm, PA, 104 W 9th
Street, Suite 400, Kansas City, Missouri 64105, USA. The other authors declare they have no
actual or potential competing financial interests.
4. 3
Abstract
Background: The economic value of unconventional natural gas resources has stimulated rapid
globalization of horizontal drilling and hydraulic fracturing. However, natural radioactivity
found in the large volumes of “produced fluids” generated by these technologies is emerging as
an international environmental health concern. Current assessments of the radioactivity
concentration in liquid wastes focus on a single element – radium. However, the use of radium
alone to predict radioactivity concentrations can greatly underestimate total levels.
Objective: We investigated the contribution to radioactivity concentrations from naturally
occurring radioactive materials (NORM), including uranium, thorium, actinium, radium, lead,
bismuth, and polonium isotopes to the total radioactivity of hydraulic fracturing wastes.
Methods: For this study we used established methods and developed new methods designed to
quantitate NORM of public health concern that may be enriched in complex brines from
hydraulic fracturing wastes. Specifically, we demonstrate the use of high purity germanium
gamma spectrometry and isotope dilution alpha spectrometry to quantitate NORM.
Results: We observed that radium decay products are initially absent from produced fluids due
to differences in solubility. However, in systems closed to the release of gaseous radon, our
model predicts that decay products will begin to ingrow immediately and (under these closed-
system conditions) can contribute to an increase in the total radioactivity for over 100 years.
Conclusions: Accurate predictions of radioactivity concentrations are critical for estimating
doses to potentially exposed individuals and the surrounding environment. These predictions
must include an understanding of the geochemistry, decay properties, and ingrowth kinetics of
radium and its decay product radionuclides.
5. 4
Introduction
New unconventional-drilling technologies (horizontal drilling combined with hydraulic
fracturing, called ‘fracking’) are unlocking vast reserves of natural gas in the United States and
around the world (EIA 2014; Cueto-Felgueroso and Juanes 2013). The potential economic value
of these reserves has stimulated a rapid globalization of the approach (Boyer et al. 2011).
However the pace of proliferation of these practices has raised concerns about the potential for
unintended and undesirable environmental impacts (Finkel 2011; Goldstein et al. 2012; Howarth
et al. 2011; Kerr 2010; Schmidt 2011; Thompson 2012). One key environmental issue associated
with unconventional drilling and hydraulic fracturing, is the management of water resources and
liquid wastes (flowback and produced fluids) (Clark and Veil 2009; Kondash et al. 2013; Lutz et
al. 2013; Vidic et al. 2013; Yang et al. 2013; Zhang et al. 2014). Of the environmental
contaminants documented in hydraulic fracturing liquid wastes, naturally occurring radioactive
materials (NORM) are of particular concern (Brown 2014; Kargbo et al. 2010; Vengosh et al.
2014).
Recent attention has focused on unintentional releases of radium (Ra) isotopes from wastewater
treatment plants (Warner et al. 2013), which can arise from incomplete treatment of high ionic
strength flowback and produced fluids (Gregory et al. 2011). For example, breakthrough of
untreated fluids at a waste treatment facility in central Pennsylvania (northeastern United States)
led to Ra contamination in stream sediments measured to be a factor of 200 greater in
radioactivity concentration than local background levels (Warner et al. 2013). The magnitude of
the Ra contamination at this site prompted the plant operator to proceed with remediation of
contaminated sediments in the surface water system (Blacklick Creek) impacted by the
discharges (Hunt 2014). Thus, NORM contamination of local environments, arising from
6. 5
improper treatment and disposal of produced fluids, could emerge as an unintended consequence
of hydraulic fracturing. Although, the potential for local populations and workers to experience
unhealthy exposures to NORM contained in such wastes is controversial (Brown 2014),
monitoring the radioactivity concentrations in these materials is critical to the development of
effective waste management strategies and exposure assessments. However, few peer-reviewed
reports are available that document levels of NORM in produced fluids. Of those available from
the Marcellus Shale (the largest shale-gas formation in the United States), most report
radioactivity concentrations of a single element — radium (Barbot et al. 2013; Haluszczak et al.
2013; Nelson et al. 2014; Rowan et al. 2011).
The naturally occurring Ra isotopes of concern (226
Ra and 228
Ra) have been reported (in peer-
reviewed literature) to exceed 670 Bq/L and 95 Bq/L, respectively in produced fluids (Barbot et
al. 2013; Haluszczak et al. 2013; Nelson et al. 2014; Rowan et al. 2011). However, little attention
has been paid to other environmentally persistent alpha- and beta-emitting NORM, such as
uranium (U); thorium (Th); radon (Rn); bismuth (Bi); lead (Pb); and polonium (Po) isotopes
(Figure 1). In a review of a report of gross alpha levels in fluids from Marcellus Shale, we
observed that reported Ra radioactivity concentrations were similar to maximum gross alpha
levels (Barbot et al. 2013), indicating that Ra had been selectively extracted into the liquid
wastes, while alpha-emitting daughters remained insoluble under the geochemical conditions of
the fluid extraction process. Given that Ra decay products had likely existed in a steady-state
radioactive equilibrium with Ra isotopes in the solid shale-formation matrix for millions of years
prior to drilling activities, these observations prompted us to explore the radioactive equilibrium
relationships of Ra decay products in produced fluids, particularly for the longer-lived alpha-
emitters, 228
Th (t1/2 = 1.91 y) and 210
Po (t1/2 = 138 d) (half-lives were extracted from NuDat 2
7. 6
Database [National Nuclear Data Center (NNDC) 2013]).
As we reported previously, the chemical composition of fluids from the Marcellus Shale can
interfere with the analysis of Ra isotopes by wet chemistry methods (Nelson et al. 2014).
However, the physicochemical properties of select alpha-emitters (210
Po, 228
Th, and certain U
isotopes) allow for chemical extraction and analysis by isotope dilution alpha spectrometry
techniques. Thus, we developed a method to analyze alpha-emitting Po, Th, and U isotopes in
produced fluids from the Marcellus Shale. Using this method (in systems closed to the release of
gaseous radon), we find that estimates of total radioactivity in produced fluids based on Ra
isotopes alone can underestimate the total radioactivity present due to the ingrowth of Ra decay-
product radionuclides, a process that we demonstrate can be modeled using radioactive ingrowth
equations (Bateman 1910). This model predicts that when produced fluids are sealed to the
release of radon gas, the total radioactivity concentration of produced fluid can increase by a
factor greater than five within the first 15 days following extraction due to the ingrowth of
radium decay products. Measurements of decay series radionuclides 210
Po and 228
Th in produced
fluids from the Marcellus Shale presented here support these predictions. Thus, estimates of the
radioactivity associated with hydraulic-fracturing liquid wastes must include projections of
ingrowth of decay product radionuclides in the natural uranium (238
U) and thorium (232
Th) decay
series.
Methods
General
The State Hygienic Laboratory (SHL) at the University of Iowa is accredited by the United
States National Environmental Laboratory Accreditation Program (NELAP). Standard operating
procedures and quality assurance measures meet those established by NELAP. All chemical
8. 7
reagents used were ACS grade or higher. All radioactivity values are decay corrected to the
reference date of 7 May, 2013 8:00 a.m. (CST). All uncertainties, unless indicated, are standard
uncertainties corresponding to one standard deviation of multiple measurements (Currie 1968).
Tracers and standards
All radioactive tracers were standard Reference Materials (SRMs) obtained from (1) the United
States National Institute of Standards and Technology (NIST), (2) NIST-traceable certified
reference materials (CRMs) obtained from Eckert & Ziegler Radioisotopes (E&Z) or Analytics
or (3) the United Kingdom National Physical Laboratory (NPL) Management Ltd. The following
sources were used: a 3 L liquid Marinelli geometry (E&Z 93474), 210
Pb (E&Z 94643), nat
U (E&Z
CRM 92564), 232
U (E&Z CRM 92403 or E&Z 7432; certified in equilibrium with 228
Th), 230
Th
(NIST SRM 4342A or Analytics 67900-294), 209
Po (NIST 4326 or E&Z CRM 92565), and
multi-line alpha-emitting sources (E&Z 91005, Analytics 59956-121, and Amersham AMR.43).
Sample description
A representative sample of produced fluids from northeastern PA (described previously) was
used for all of the following experiments (Nelson et al. 2014). A 200 L drum of Marcellus Shale
produced fluids was received at the SHL on May 7, 2013. The sample originated from a well that
was horizontally drilled to a depth of 2100 m and fractured with approximately 35,000 m3
of
hydraulic fracturing fluid in early 2012. Analysts at SHL characterized the elemental
composition using standard techniques.
High purity germanium (HPGe) gamma spectrometry
HPGe gamma spectrometry of produced fluids was conducted as previously described (Nelson et
al. 2014). Briefly, we calibrated our detector to a 3 L liquid Marinelli geometry (E&Z 93474)
9. 8
using standard practices. To calibrate for the low energy gamma emission of 210
Pb, we counted a
3 L Marinelli beaker spiked with 210
Pb of known activity (E&Z 94643). This spectrum was
merged with the detector calibration using standard features available in ORTEC Gamma Vision
(Version 6.08, analysis engine Env32). Quality assurance and quality control (QA/QC) measures
included weekly background counts, and linearity and efficiency checks collected three times per
week. A 3 L sample was homogenized by heating with 51 g of Bacto Agar (BD 214010) and
allowed to cool in a 3 L Marinelli beaker. The sample was then counted for 17 hours on a 30%
efficient ORTEC HPGe. Spectral analysis was preformed using ORTEC Gamma Vision
(Version 6.08) with a library of radionuclides created in GammaVision Library Editor according
to the manufacturer recommendations. All emission energies, half-lives (with exception of
209
Po), and their uncertainties were extracted from the NuDat 2 Database [NNDC 2013] and
include evaluated nuclear data at of the time of analysis. The sole exception was the half-life of
209
Po for which we chose to use 128.3 years (Collé et al. 2007). Data are presented in Table 2.
Alpha-emitting radionuclides
Analysis of produced fluids for alpha-particle emitting radionuclides in the 238
U and 232
Th decay
series (210
Po, 228
Th, 230
Th, 234
U, 235
U, 238
U) was conducted by preconcentration and isotope
dilution alpha spectrometry as described below. All results presented are from an unfiltered
subsample (20 L, polypropylene carboy) drawn from the homogenized 200 L barrel. The barrel
was hermetically sealed following each subsampling for the results reported here. The subsample
pH was adjusted to 2 and held (approximately 48 h) to allow iron-rich particulate to dissolve to a
transparent, yellowish acidified solution. Pre-concentration and matrix simplification was then
conducted via co-precipitation of Po, Th, and U with endogenous iron (Fe) as the hydroxide
Fe(OH)3 and added manganese (Mn) for co-precipitation as manganese dioxide (MnO2), as
10. 9
previously described (Eichrom 2009; Harada et al. 1989). Preliminary experiments demonstrated
exceedingly low concentrations of 230
Th, allowing use of 230
Th as a radiotracer to determine
yields and concentration of 228
Th. Following pre-concentration and matrix simplification (via
metal oxide/hydroxide co-precipitation; i.e., Fe(OH)3 and MnO2), Po, U, and Th were separated
into radiochemically-pure fractions via extraction chromatography described below.
MnO2 coprecipitations
Samples were spiked with 150 to 500 mBq of 209
Po, 230
Th, 232
U, nat
U. After appropriate tracers
were added, MnO2 coprecipitations were performed, based on published methods (Burnett et al.
2012; Moore 1976; Nour et al. 2004). KMnO4 (15 or 30 mg) and bromocresol purple (1 mL,
0.1%) were added to acidified (pH < 2) produced fluid (0.5 L) in glass beakers. The sample was
diluted twofold (dH2O), covered with a watch glass, and boiled (1 h). The pH was adjusted to 7-
8, the sample was boiled (1 h), and cooled overnight. Following the cooling period, the
supernatant was aspirated and the remaining slurry (~50 mL) was transferred to a plastic conical
tube (50 mL), centrifuged (10 min), and the supernatant was discarded. Beakers were washed
twice (5 mL, 6 M HCl; 1 mL, 1 M ascorbic acid); each time transferring wash to the 50 mL
centrifuge tube to dissolve the MnO2 pellets. Centrifuge tubes were then gently heated in a water
bath to fully dissolve pellet and clarify the solution.
Method 1: SR resin and Ag autodeposition separation of polonium
In some cases (see Table 1), Po isotopes were isolated by Eichrom method Lead-210 and
Polonium-210 in Water (OTW01 Rev. 2.0) (Eichrom 2009). Briefly, samples were spiked with
209
Po prior to MnO2 or Fe(OH)3 precipitation. Precipitates were dissolved (10 mL, 2 M HCl),
reduced (1 mL, 1 M ascorbic acid), and gently heated in a water bath. Solutions were then loaded
onto preconditioned Eichrom SR Resin (10 mL, 2 M HCl). Columns were rinsed (10 mL, 2 M
11. 10
HCl) to remove trace contaminants. Po was then eluted with two additions of acid (5 mL, 1 M
HNO3; 15 mL, 0.1 M HNO3). Eluent was wet ashed (0.5 M HCl) under lower heat with to
remove HNO3. Samples were then dissolved (40 mL, 0.5 M HCl) and reduced (100 mg ascorbic
acid). Po was then allowed to autodeposit overnight at 80°C onto silver (Ag) disks painted on
one side with acid-resistant acrylic paint. Disks were then cleaned (~10 mL 0.5 M HCl, dH2O,
ethanol, and acetone, in that order) and dried prior to alpha spectrometry.
Method 2: TRU-Ag-TEVA separation (final method)
After MnO2 coprecipitation and solubilization, most samples (see Table 1) were loaded onto
preconditioned TRU cartridges (10 mL, 4 M HCl) to adhere Po, U and Th (Horwitz et al. 1993).
TRU resin was washed three times (5 mL, 4 M HCl) before eluting Po, U, and Th (10 mL, 0.1 M
ammonium bioxalate) into 150 mL glass beakers containing approximately 20 mL of 0.1 M HCl.
The eluent was then reduced to prevent interferences from iron (0.5 mL, 20% w/v
hydroxylamineŸHCl; 0.1 mL, 1 M ascorbic) (Manickam et al. 2010). Samples were incubated
(90°C) in a double boiler on a stir plate. A magnetic stir bar and a polished Ag disk (one side
coated with acid-resistant acrylic spray-paint) were placed into the beaker. After 2.5 h, disks
were removed and washed (10 mL each 0.1 M HCl, H2O, ethanol, and acetone, in that order).
The remaining solution was taken to dryness and resuspended (10 mL, 4 M HCl). U and Th were
then separated on TEVA using a method developed in our laboratory (Knight et al. 2014). The
solution of 4 M HCl containing U and Th was loaded onto a preconditioned TEVA column (10
mL, 4 M HCl). Th does not adhere to the column in these conditions. Therefore, Th was
collected in the eluent of the load solution along with an additional column wash (10 mL, 4 M
HCl). The column was then washed (25 mL, 4 M HCl) to remove trace Th before U was eluted
(5 mL, 0.1 M HCl). Th was precipitated by a rare-earth hydroxide as follows: cerium (Ce, 30
12. 11
µg), bromocresol purple (1 mL, 0.1%), and H2O2 (30 µL, 30%). The pH was adjusted to 7 with
ammonium hydroxide and left undisturbed (30 min). U sources were prepared by a rare-earth
fluoride precipitation by addition of Ce (50 µg), titanium trichloride (1 mL), and hydrofluoric
acid (1 mL). U and Th samples were filtered on Eichrom Resolve Filters according to
manufacturer’s recommendation. For workflow schematic, see Supplemental Material, Figure
S1.
Method 3: TRU-TEVA for separation of U and Th
Reported activities of U (Table 1) in the produced fluids were determined using a method
previously developed in our laboratory (Knight et al. 2014). This method differs only slightly
from those described above. The pellets were dissolved in HNO3 (10 mL, 2 M) and TRU resin
was preconditioned and washed with HNO3 (10 mL, 2 M) en lieu of HCl. This method was
investigated but abandoned, as it does not allow for analysis of 210
Po.
Isotope dilution alpha spectrometry
All alpha sources were quantitated by standard isotope dilution techniques and counted in
vacuum controlled α-spectrometers (Alpha Analyst, Canberra or Alpha Ensemble; ORTEC) as
previously described (Knight et al. 2014). Briefly, source-to-detector distances were usually 10
mm, corresponding to a counting efficiency of approximately 18-30%. In some instances, the
distance was increased to improve resolution. Radiochemical yields were determined by standard
protocols using efficiencies calculated with a NIST traceable, multi-line α-spectrometry standard
source (E&Z 91005 or Analytics 59956-121). For all samples, thin films were used to prevent
daughter recoil contamination of detectors (Inn et al. 2008). Sources were counted for 17 to 200
hours, as necessary. Standard isotope dilution techniques were used to calculate the activity and
recoveries of added controls. In samples where 232
U and 230
Th were used, activity of 228
Th
13. 12
introduced from the 232
U tracer was subtracted using yield determinations for Th isotopes
calculated by 230
Th. QA/QC included blanks (no added tracers) and laboratory control spikes
(LCS). Data are presented in Table 1.
Radioactive ingrowth modeling
Radioactive ingrowth was modeled generally according to the Bateman equation (Bateman
1910) and solved in Microsoft Excel. The derivation and formatting of the Bateman equation
was obtained from a previously published source (Choppin et al. 2002).
Results
Radiochemical disequilibria and ingrowth
Radiochemical yields for the final methodology were: Po (81±6%); U (63±8%); Th (85±9 %). In
this study, the observed concentrations of natural U (238
U, 235
U, 234
U), and Th isotopes (234
Th,
232
Th, and 230
Th) were exceedingly low (< 5 mBq/L). These levels represented less than 0.001%
of the 226
Ra radioactivity concentration (670 ± 26 Bq/L; 186 keV peak) in this sample of
produced fluids described previously (Nelson et al. 2014). Similarly, we found that the
radioactivity concentrations of Ra decay products, including 228
Th, 214
Pb, 214
Bi, 212
Pb, 210
Pb,
210
Po, and 208
Tl, were initially near detection limits (Figure 2A, 2B, 2C, 2D, Table 1, Table 2).
On the other hand, subsequent analysis of the same sample of produced fluids over time revealed
an increase in the radioactivity concentration of decay products 210
Po and 228
Th, which are
supported by 226
Ra and 228
Ra, respectively (Figure 1; Figure 2A, 2B). Importantly, the storage
drum was hermetically sealed between subsamplings for analysis of radioactive decay products
to prevent the release of gaseous radon. Notably, under these conditions, the observed increase in
radioactivity concentration of 210
Po and 228
Th followed an established radioactive ingrowth
model (Bateman equation), which describes the ingrowth of decay products following a
14. 13
separation (radioactive disequilibrium) of decay products from the parent radionuclide at time
zero (t0). From these observations we developed a theoretical model for the geochemical
partitioning of NORM in the Marcellus Shale formation, within the context of hydraulic
fracturing and associated waste disposal activities (Figure 3). This model serves as a guide for
predicting the partitioning and radioactive ingrowth/decay of NORM in the environment
surrounding unconventional drilling and hydraulic fracturing operations, as well as in the waste
treatment and disposal setting. Importantly, the ultimate fate and transport of NORM in the
surface and subsurface environment is site dependent; depends also on the potential for release of
radon gas; and assessment of the ultimate fate and transport of NORM must be examined on an
individual site basis.
Discussion
Modeling the partitioning NORM in Marcellus Shale
The partitioning U and Th decay series radionuclides in Marcellus Shale liquid wastes is a
function of elemental geochemical behavior ⎯ linked with key biogeochemical features of the
formation. Like many marine black-shale formations, the Marcellus Shale is an ancient seabed
that became enriched in U associated with organic matter (Carter et al. 2011; Kargbo et al. 2010;
Swanson 1961). Produced fluids from the Marcellus Shale have characteristically high levels of
salts, the origin of which has several explanations (Blauch et al. 2009). There are notably low
levels of sulfate (SO4
2-
) (Osborn and McIntosh 2010), likely due to microbial processes that
produce sulfides (S2-
) (Libes 1992). The ionic strength, reducing environment, and low
abundance of SO4
2-
alter the potential for NORM to solubilize in produced fluids. For example,
low levels of SO4
2-
and relatively high ionic strength enhance the solubility of Ra, while reducing
conditions promote precipitation of geochemical species of reduced U, i.e., U(IV). Radium decay
15. 14
product radionuclides, such as Pb and Po are also much more particle reactive and less likely to
be extracted through the unconventional drilling and hydraulic fracturing process than decay-
series parent Ra isotopes. Thus, differences in the speciation of the elements in the natural decay
series govern the likely concentration that will be observed in liquid wastes (as they emerge from
depth), following an unconventional drilling and hydraulic fracturing event.
232
Th Series partitioning
The parent and supporting isotope in the natural Th decay series, 232
Th (t1/2 = 1.4 x 1010
y), is not
expected to undergo oxidation/reduction reactions under natural conditions at depth in the
formation, but is nonetheless particle reactive and insoluble in environmental waters and brines
(Melson et al. 2003). Accordingly, we observed exceedingly low concentrations of 232
Th in
unfiltered Marcellus Shale produced fluids. However, the decay of 232
Th produces highly soluble
divalent alkaline earth 228
Ra (t1/2 = 5.75 y), which has likely been in radioactive secular
equilibrium (steady-state) with 232
Th for many millions of years (Gonneea et al. 2008). As a
result, produced fluids are enriched in 228
Ra (relative to 232
Th), which is highly soluble in the
high-salt-content brines that describe produced fluids. 228
Ra decays by beta-emission to short
lived 228
Ac (t1/2 = 6.15 h), which likely forms insoluble complexes and quickly adsorbs to
mineral surfaces at depth ⎯ and decays rapidly to form highly-insoluble alpha-particle emitting
radionuclide 228
Th (t1/2 = 1.91 years) (Hammond et al. 1988). Similar to other Th isotopes, 228
Th
is insoluble in interstitial fluids of shale formations, and its concentration is also observed to be
low in produced fluids as they emerge from depth. Notably, the large difference in solubility
between 228
Ra and 228
Th gives rise to a chronometer that has the potential to determine the time
when fluids were extracted from the Marcellus Shale (for more information, see Supplementary
Material, Expanded Methods, Thorium-228 Ingrowth). As 228
Th ingrows at a rate related to its
16. 15
half-life, its decay product 224
Ra (t1/2 = 3.63 days), rapidly ingrows to steady-state radioactive
equilibrium. Rapid ingrowth of 224
Ra is followed by a series of short-lived radioactive decay
products that ultimately decay to stable 208
Pb (Figure 1). Within this series of relatively short-
lived decay products, gaseous 220
Rn (t1/2 = 55.6 s) presents a potential challenge to modeling
expected increases in total radioactivity resulting from radioactive ingrowth processes. On the
other hand, because the half-life of 220
Rn is so short, migration beyond the immediate vicinity of
nuclear formation is likely minimal and disequilibrium is not expected. Thus, in this decay
series, the modeled-total 228
Ra-supported radioactivity concentration in produced fluids has the
potential to increase to a maximum within 5 years of extraction from the shale formation,
followed by a decrease determined by the half-life of 228
Ra (t1/2 = 5.75 y) (Figure 4A and 4B).
This suggests that inclusion of the ingrowth and decay of 228
Ra decay products (particularly
228
Th) is important for development of appropriate liquid waste management.
238
U series partitioning
Owing to the geologic history and reducing (anoxic) conditions at depth in the Marcellus Shale
formation, parent and supporting radionuclide 238
U (which, unlike 232
Th can be redox active
under natural conditions) is likely to be contained in the crystal lattice of minerals or adsorbed to
solid phase structures in a reduced highly-insoluble (+4) oxidation state (Swanson 1961) (Figure
1; Figure 3). Thus, geochemical conditions favor adsorption of 238
U and decay-product actinides
(234
Th, 234
Pa, and 234
U) to interstitial surfaces of surrounding minerals (Figure 1; Figure 3)
(Melson et al. 2003), and these radionuclides are likely fixed at depth. In support of these
assertions, we observed exceedingly low concentrations of U and Th radionuclides in unfiltered
produced fluids from Marcellus Shale (Table 1, Table 2). Analysis of alpha spectra further
revealed an apparent enrichment of 234
U (relative to 238
U) in produced fluids, which can likely be
17. 16
explained by alpha-recoil processes (Figure 2E and 2F) (Fleischer 1980; Osmond et al. 1983).
Further investigations of partitioning among relevant phases (filtered/ultrafiltered aqueous,
particulate, and solid) will provide more detailed understanding of the speciation of actinides in
unconventional drilling liquid wastes.
In contrast to low solubility of 238
U-series actinides in produced fluids, 238
U decay-product
radionuclide 226
Ra (t1/2 = 1600 y) is highly soluble in such fluids. Thus, 226
Ra becomes enriched
in the aqueous phase at depth relative to supporting actinides, with which 226
Ra has likely been in
secular equilibrium (steady-state) for many millions of years (Gonneea et al. 2008). Decay
product radionuclides of 226
Ra are concerning due to the long half-life of 226
Ra, which ensures
natural production (via radioactive ingrowth) of decay products for thousands of years (Figure
4C, 4D, 4E, and 4F). While 226
Ra is highly soluble in produced fluids, our observations suggest
that 226
Ra decay product radionuclides (Figure 1;Figure 3) are relatively insoluble under these
conditions and are retained at depth by interactions with mineral phases in the interstitial
environment. Although this geochemical behavior results in very low concentration of 226
Ra
decay products as fluids emerge from depth, the Bateman radioactivity ingrowth equations
predict that (in systems closed to the release of gaseous 222
Rn) the total 226
Ra-supported
radioactivity concentration in produced fluids can increase by a factor greater than five (alpha-
particle emissions by a factor of approximately four) over a period of 15 days following
extraction of produced fluids (Figure 4D). Importantly, radioactive ingrowth will continue for
decades as longer-lived isotopes (210
Pb, t1/2 = 22 y; 210
Po, t1/2 = 138 d) approach radioactive
equilibrium with 226
Ra (at a rate related to their own half-lives; Figure 4E). As an example, we
compared the Bateman-equation-based radioactivity ingrowth model to the observed
radioactivity concentration of alpha-emitting radionuclide 210
Po in sequential analyses of
18. 17
unfiltered-acidified produced fluids from Marcellus Shale that were stored in a hermetically
sealed container for several months. The observed increase in radioactivity concentrations of
210
Po in this sample followed the predicted ingrowth under the conditions described (Figure 2A).
Ingrowth of long-lived radioactive 210
Pb and 210
Po is important to overall risk assessments in this
context because these radionuclides are potentially bioavailable and may accumulate in higher
organisms (Bacon et al. 1988; Cherrier et al. 1995; Fisher et al. 1983; Heyraud and Cherry 1983).
Thus, the use of 226
Ra alone to predict total radioactivity concentration in liquid drilling wastes
can underestimate the increase in levels that will occur over time and neglects the potential for
the bioaccumulation of alpha- and beta-emitting decay product radionuclides in bacteria, plants,
and higher organisms.
Similar to the decay product scenario of Th-series Ra isotope 228
Ra, establishing radioactive
equilibrium of decay product radionuclides with parent 226
Ra is potentially confounded by the
presence of a gaseous isotope (i.e., 222
Rn, t1/2 = 3.82 d) in the decay series. Further, in this case
the half-life of 222
Rn is sufficiently long to potentially promote migration and separation
(disequilibrium) from parent 226
Ra in systems that are open to the atmosphere (e.g., containment
ponds; Figure 3). In these cases, the modeled concentration of 226
Ra decay products will need to
include an assessment of 222
Rn emanation and decay to accurately portray the total concentration
in liquid drilling wastes and the impact of increased 222
Rn and decay products to surroundings.
Conclusion
Previous reports that describe the radioactivity concentration in flowback, produced fluids, and
other materials associated with unconventional drilling and hydraulic fracturing have focused on
one element – Ra. Our projections suggest that in systems closed to the release of gaseous Rn,
estimates based solely on 226
Ra/228
Ra will underestimate the total activity present by a factor
19. 18
greater than five within 15 days following extraction as Ra decay product radionuclides ingrow.
The level of radioactivity (in a closed 226
Ra decay product system) will continue to increase and
reach a maximum approximately 100 years after extraction (Figure 4F). At this time, when the
long-lived 210
Pb and its decay products have reached equilibrium with 226
Ra, the total
radioactivity will have increased by a factor greater than eight. While this projection assumes
losses of Rn and other geochemically derived disequilibria are negligible, the physical process of
ingrowth begins again at any time of Ra separation (e.g., sulfate treatment at wastewater
treatment plants) and the total activity unavoidably increases as decay product radionuclides
ingrow. Thus, long-lived, environmentally persistent Ra decay products (228
Th, 210
Pb, 210
Po)
should be considered carefully as government regulators and waste handlers assess the potential
for radioactive contamination and exposures.
NORM is emerging as a contaminant of concern in hydraulic fracturing/unconventional drilling
wastes, yet the extent of the hazard is currently unknown. Sound waste management strategies
for both solid and liquid hydraulic fracturing and unconventional drilling waste should consider
the dynamic nature of radioactive materials. Methods designed to remove Ra from hydraulic
fracturing waste may not remove Ra decay products, as these elements (Ac, Th, Pb, Bi, Po
isotopes) have fundamentally different physicochemical properties (Kondash et al. 2013; Zhang
et al. 2014). Future studies and risk assessments should include Ra decay products in assessing
the potential for environmental contamination in recreational, agricultural, and residential areas,
as well as in developing a more detailed understanding of the accumulation of these
radionuclides in higher organisms.
20. 19
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25. 24
Table 1. Alpha spectrometry of produced fluids. Recoveries, activities, and separation method
for select radioisotopes.
Isotope Activity (mBq/L) Standard
Deviation of
Activity
(mBq/L)
a
Recovery (%) Standard
Deviation
of
Recovery
(%)
b
Days
c
n Method
d
210
Po 151 3 42 11 21 3 1
388 12 28 2 50 3 1
596 10 13 2 70 3 1
1000 24 84 6 99 4 2
4130 40 77 5 278 4 2
228
Th 5750 140 71 2 66 4 2
6900 23 87 7 99 4 2
22020 850 87 9 278 4 2
232
U N/A N/A 60 3 99 3 2
N/A N/A 69 8 278 3 2
238
U 1.13 0.17 70 3 28 3 3
235
U 0.14 0.05 70 3 28 3 3
234
U 2.58 0.88 70 3 28 3 3
a
Standard deviation of multiple counts. b
Standard deviation of multiple counts. c
After 8 a.m. on 7 May
2013 (CST). d
1 = Sr-Ag Autodeposition, 2 = TRU-Ag-TEVA, 3 = TRU-TEVA.
26. 25
Table 2. HPGe gamma spectrometry of produced fluids. HPGe analysis of 3 L produced fluids
homogenized with BactoAgar in a 3 L Marinelli beaker.
Isotope Activity
(Bq/L)
Uncertainty
(Bq/L)
a
CL
(Bq/L)
b,c
Peaks (keV)
228
Ac 76 1 0.6 911, 338
224
Ra 21 3 3 241
212
Pb 2.4 0.3 0.2 239
208
Tl <CL N/A 1 860
234m
Pa <CL N/A 13 1001
234
Th <CL N/A 7 63
226
Ra 670 3 3 186
214
Pb 256 2 0.8 295, 242, 580, 480
214
Bi 235 1 0.3 609, 1120,1238, 768, 934, 1385, 1583, 274
210
Pb <CL N/A 20 46
40
K 10 1 1 1461
a
Uncertainties are GammaVision generated counting uncertainties. b
At time of acquisition 2:18 PM (CST)
on 15 May 2013. c
Critical level (CL) determined by the Currie Limit
27. 26
Figure Legends
Figure 1. Natural thorium and uranium decay chains. Half-lives and decay information from the
NuDat 2 Database [NNDC 2013].
Figure 2. Po, Th, and U activities and alpha spectra. (A) Theoretical Bateman model of 210
Pb
ingrowth (blue) and 210
Po (red) given 226
Ra levels and a system closed to emanation of gaseous
radon in produced fluids sample with our empirical data (black squares, error bars subsumed
within boxes). (B) Theoretical Bateman model of 228
Th ingrowth (green) and 228
Ra decay (blue)
given 228
Ra levels and a system closed to emanation of gaseous radon in produced fluids sample
with our empirical data in black (error bars subsumed within boxes). (C) Representative Po alpha
spectrum of 209
Po tracer (orange) and 210
Po (red). (D) Representative Th alpha spectrum of 230
Th
tracer (purple), 228
Th (green), and 228
Th decay products (black). 232
Th was virtually undetectable
by this method. (E) Activities of 238
U (purple), 235
U (black), and 234
U (orange) in produced fluids
with error bars representing one standard deviation of the determined activity of multiple counts
(n=3). (F) Representative U alpha spectrum of 238
U (purple), 235
U (not labeled), 234
U, 232
U tracer
(blue) and 232
U tracer decay products (228
Th green, others black).
Figure 3. Partitioning of NORM in Marcellus Shale and associated waste. Theoretical model of
NORM partitioning based on HPGe gamma spectrometry and alpha spectrometry of produced
fluids. Solid arrows indicate a radioactive decay or series of radioactive decays. Dashed arrows
indicate a physical or chemical partitioning process.
Figure 4. Ingrowth of radium decay products. Theoretical Bateman model of Ra decay product
ingrowth and decay (system closed to release of gaseous radon). (A) 15 days after extraction for
228
Ra (green dots), associated alpha (red dashes) and total activity (blue); (B) 70 years after
extraction for 228
Ra (green dots), associated alpha (red dashes) and total activity (blue); (C) 70
years after extraction for 226
Ra (purple), 228
Ra (green dots), associated alpha (red dashes) and
total activity (blue); (D) 15 days after extraction for 226
Ra (purple), associated alpha (red dashes)
and total activity (blue); (E) 70 years after extraction for 226
Ra (purple), associated alpha (red
dashes) and total activity (blue); (F) 5000 years after extraction for 226
Ra (purple), associated
alpha (red dashes) and total activity (blue).