Nuclear magnetic resonance logging: Example applications of an emerging tool for environmental investigations

Nuclear magnetic resonance (NMR) geophysical tools have been widely used in the petroleum exploration industry since the 1960s and have improved significantly in the last two decades. These tools can provide estimates of bulk porosity and fluid content, quantification of bound versus mobile fluids, and estimates of hydraulic conductivity (K). Although the size and cost of oil‐field tools historically limited their use for near‐surface applications, smaller and more economical downhole NMR logging tools are now available for detecting and characterizing the formation water content and K to support environmental and groundwater resource investigations. These tools can be deployed using direct‐push drilling techniques or they can be lowered into existing open borings or wells with nonconductive polyvinyl chloride casings and screens. In many cases, using the tool in existing wells offers a safer and more cost‐effective alternative compared to drilling new boreholes. For environmental investigations, NMR can provide useful high‐resolution quantitative hydrostratigraphic information that can provide additional valuable data to further inform and refine the conceptual site model. This paper highlights several NMR field investigations that demonstrate the viability of this technology as a site characterization tool for near‐surface investigations. NMR measurements were compared to data from lithologic logs, cone penetrometer testing data, and prior field hydraulic tests. Use of NMR to detect vadose zone water, including previously unidentified perched groundwater zones, provided hydrostratigraphic details that could not be gleaned from historical well drilling logs and were used to evaluate drainable pore water versus pore water bound in small pores by capillary forces or electrochemically clay‐bond water. NMR also produced K estimates similar to those from conventional hydraulic tests, but the improved vertical resolution from NMR provided additional information regarding the vertical heterogeneity of the formation along the entire length of the well or borehole. Additionally, bench‐scale tests are presented that confirm the capability for NMR to reliably detect and quantify light nonaqueous phase liquid saturation (specifically diesel fuel and weathered gasoline) in situ. The field tests combined with bench‐scale testing results affirm the applicability and potential for NMR as a practical characterization tool that should increasingly be utilized in environmental investigations.     

Relative effect of soil moisture on emissions and distribution of 1,3-dichloro-propene and chloropicrin in soil columns

Emissions of soil fumigants are regulated to protect air quality in California. Irrigation prior to fumigation can reduce fumigant emissions at relatively low costs; however, the optimum range of soil water content that reduces emissions without reducing efficacy is not clearly defined. The objective of this study was to determine the effects of soil water content [at 30, 45, 60, 75, 90 and 100% field capacity (FC)] on the emission and distribution of fumigants 1,3-dichloropropene (1,3-D) and chloropicrin (CP) in columns packed with a sandy loam soil. After injecting equal amounts of cis-1,3-D, trans-1,3-D, and CP, fumigant emissions and distribution in soil were monitored for 14 days. Emissions of all three compounds showed similar response to soil water content except that CP emissions were lower than both isomers of 1,3-D. The emission peak flux was highest and occurred earliest in the driest soil while it was reduced and delayed as soil water content increased. After the peak, emission flux decreased rapidly in the driest soil but more slowly in higher water content treatments. Initially, higher soil water content resulted in substantially lower cumulative emissions among the treatments, but as time progressed, the differences in cumulative emissions decreased or even disappeared. These trends were likely due to the effect of the closed-bottom short soil columns which allowed fumigants to only move upward and contribute to emission. Higher fumigant concentrations in the soil–gas phase were observed in high soil water content treatments, due to less emission loss and more fumigant retained in the soil.     

Lagrangian sampling of 3-D air quality model results for regional transport contributions to sulfate aerosol concentrations at Baltimore,MD, in summer 2004

We use ensemble-mean Lagrangian sampling of a 3-D Eulerian air quality model, CMAQ, together with ground-based ambient monitors data from several air monitoring networks and satellite (MODIS) observations to provide source apportionment and regional transport vs. local contributions to sulfate aerosol and PM_2.5 concentrations at Baltimore, MD, for summer 2004. The Lagrangian method provides estimates of the chemical and physical evolution of air arriving in the daytime boundary layer at Baltimore. Study results indicate a dominant role for regional transport contributions on those days when sulfate air pollution is highest in Baltimore, with a principal transport pathway from the Ohio River Valley (ORV) through southern Pennsylvania and Maryland, consistent with earlier studies. Thus, reductions in sulfur emissions from the ORV under the EPA's Clean Air Interstate Rule may be expected to improve particulate air quality in Baltimore during summer. The Lagrangian sampling of CMAQ offers an inexpensive and complimentary approach to traditional methods of source apportionment based on multivariate observational data analysis, and air quality model emissions separation. This study serves as a prototype for the method applied to Baltimore. EPA is establishing a system to allow air quality planners to readily produce and access equivalent results for locations of their choice.     

Polybrominated diphenyl ethers and polybrominated biphenyls in Australian sewage sludge

This paper presents a brief review of the international scientific literature of polybrominated diphenyl ethers (PBDEs) and polybrominated biphenyls (PBBs) in sewage sludge and a survey of these compounds in sewage sludge from 16 Australian wastewater treatment plants (WWTPs). The SigmaPBDE mean concentration in the Australian study was 1137microgkg(-1) dry weight (d.w.) (s.d. 1116) and ranged between 5 and 4 230microgkg(-1)d.w. The urban mean of 1308microgkg(-1) (s.d. 1320) and the rural mean of 911microgkg(-1) (s.d. 831) are not statistically different and are similar to levels in European sludges. Principal components analysis was performed on the data set and revealed that 76% of the data variation could be explained by two components that corresponded to overall concentration of the pentaBDE and the decaBDE commercial formulations. An analysis of variance was performed comparing PBDEs levels at three WWTPs over the years 2005 and 2006, finding differences between treatment plants (BDE-47) but no significant difference in PBDE levels in the years 2005 and 2006. Low levels of BB-153 were detected in all samples of this survey (n=16); mean 0.6microgkg(-1)d.w. (s.d. 0.5). This compound has rarely been reported in any other study of sewage sludges undertaken outside Australia. This work highlights the need for a risk assessment of PBDEs in sewage sludge when used for land application, taking into account typical levels found in Australian sludges and soils.     

Development and implementation of coral reef biocriteria in U.S. jurisdictions

Coral reefs worldwide are declining at an alarming rate and are under continuous threat from both natural and anthropogenic environmental stressors. Warmer sea temperatures attributed to global climate change and numerous human activities at local scales place these valuable ecosystems at risk. Reefs provide numerous services, including shoreline protection, fishing, tourism and biological diversity, which are lost through physical damage, overfishing, and pollution. Pollution can be controlled under provisions of the Clean Water Act, but these options have not been fully employed to protect coral reefs. No U.S. jurisdiction has implemented coral reef biocriteria, which are narrative or quantitative water quality standards based on the condition of a biological resource or assemblage. The President’s Ocean Action Plan directs the U.S. Environmental Protection Agency (EPA) to develop biological assessment methods and biological criteria for evaluating and maintaining the health of coral reef ecosystems. EPA has formed the Coral Reef Biocriteria Working Group (CRBWG) to foster development of coral reef biocriteria through focused research, evaluation and communication among Agency partners and U.S. jurisdictions. Ongoing CRBWG activities include development and evaluation of a rapid bioassessment protocol for application in biocriteria programs; development of a survey design and monitoring strategy for the U.S. Virgin Islands; comprehensive reviews of biocriteria approaches proposed by states and territories; and assembly of data from a variety of monitoring programs for additional metrics. Guidance documents are being prepared to assist U.S. jurisdictions in reaching protective and defensible biocriteria.     

Speciation/fractionation of nickel in airborne particulate matter: improvements in the Zatka sequential leaching procedure

Modifications are reported to the sequential leaching analytical method for nickel speciation/fractionation specified by Zatka so that larger sample masses can be analyzed. Improvements have been made in the completeness of the sulfide/metallic separation during the peroxide-citrate leach step by use of a larger volume of leachant, a longer leach duration and an orbital shaker. Minimal extraction of metallic nickel in this prolonged sulfidic nickel extraction has been confirmed. An increase in the number of samples analyzed simultaneously using these modifications has resulted in substantial productivity improvements and concomitant lower costs. It is critical for practitioners of sequential leaching techniques to recognize potential limitations and to use professional judgment when interpreting results. For example, results obtained may not be biologically relevant in assessing health risks; the acts of sampling and storage may result in changes in fractionation with time; surface coatings/films may alter the ability of a leachant to react with the target compound; and leaching behaviours may be different for samples differing only in particle size distributions.     

Influence of nutrition in PCB-induced vascular inflammation

The nutritional profile of an individual can influence the toxicity of persistent environmental toxicants. Polychlorinated biphenyls (PCBs), prevalent environmental pollutants, are highly lipid-soluble toxic compounds that biomagnify through trophic levels and pose cancer, neurocognitive, and atherosclerotic risk to human populations. There is a growing body of knowledge that PCBs can initiate inflammatory responses in vivo, and this inflammation can be either exacerbated or ameliorated by nutrition. Data indicate that diets high in certain dietary lipids such as omega-6 fatty acids can worsen PCB-induced vascular toxicity while diets enriched with bioactive food components such as polyphenols and omega-3 polyunsaturated fatty acids can improve the toxicant-induced inflammation. There is evidence that bioactive nutrients protect through multiple cell signaling pathways, but we have shown that lipid raft caveolae and the antioxidant defense controller nuclear factor (erythroid-derived 2)-like 2 (Nrf2) both play a predominant role in nutritional modulation of PCB-induced vascular toxicity. Interestingly, there appears to be an intimate cross-talk between caveolae-related proteins and cellular Nrf2, and focusing on the use of specific bioactive food components that simultaneously alter both pathways may produce a more effective and efficient cytoprotective response to toxicant exposure. The use of nutrition as a protective tool is an economically beneficial means to address the toxicity of persistent environmental toxicants and may become a sensible means to protect human populations from PCB-induced vascular inflammation and associated chronic diseases.     

Fog Chemistry at an Urban Midwestern Site

This work investigates the oxidative aging of preformed secondary organic aerosol (SOA) derived from α-pinene ozonolysis (～100 ppb_v hydrocarbon [HC_x] with excess of O₃) within the University of California–Riverside Center for Environmental Research and Technology environmental chamber that occurs after introduction of additional hydroxyl (OH) and nitrate (NO₃) radicals. Simultaneous measurements of SOA volume concentration, hygroscopicity, particle density, and elemental chemical composition (C:O:H) reveal increased particle wall-loss-corrected SOA formation (1.5%, 7.5%, and 15.1%), increase in oxygen-to-carbon ratio (O/C; 15.6%, 8.7%, and 8.7%), and hydrophilicity (4.2%, 7.4%, and 1.4%) after addition of NO (ultraviolet [UV] on), H₂O₂ (UV on), and N₂O₅ (dark), respectively. The processing observed as an increase in O/C and hydrophilicity is attributed to OH and NO₃ reactions with first-generation vapor products and UV photolysis. The rate of increase in O/C appears to be only sufficient to achieve semivolatile oxygenated organic aerosol (SV-OOA) on a day time scale even at the raised chamber radical concentrations. The additional processing with UV irradiation without addition of NO, H₂O₂, or N₂O₅ is observed, adding 5.5% wall-loss-corrected volume. The photolysis-only processing is attributed to additional OH generated from photolysis of the nitrous acid (HONO) offgasing from chamber walls. This finding indicates that OH and NO₃ radicals can further alter the chemical composition of SOA from α-pinene ozonolysis, which is proved to consist of first-generation products.

Implications: Secondary organic aerosol (SOA) may undergo aging processes once formed in the atmosphere, thereby altering the physicochemical and toxic properties of aerosol. This study discusses SOA aging of a major biogenic volatile organic compound (VOC; α-pinene) after it initially forms SOA. Aging of the α-pinene ozonolysis system by OH (through NO or H₂O₂ injection), NO₃ (through N₂O₅ injection), and photolysis is observed. Although the reaction rate appears to be only sufficient to achieve semivolatile oxygenated organic aerosol (SV-OOA) level of oxygenation on a 1-day scale, it is important that SOA aging be considered in ambient air quality models. Aging in this study is attributed to further oxidation of gas-phase oxidation products of α-pinene ozonolysis.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air &; Waste Management Association for information on the referenced α-pinene ozonolysis reaction and chamber reactor temperature.