Nicholas A. Azzolina

Methane concentrations in water wells unrelated to proximity to existing oil and gas wells in northeastern Pennsylvania.

Recent studies in northeastern Pennsylvania report higher concentrations of dissolved methane in domestic water wells associated with proximity to nearby gas-producing wells [ Osborn et al. Proc. Natl. Acad. Sci. U. S. A. 2011 , 108 , 8172 ] and [ Jackson et al. Proc. Natl. Acad. Sci. U. S. A. , 2013 , 110 , 11250 ]. We test this possible association by using Chesapeake Energys baseline data set of over 11,300 dissolved methane analyses from domestic water wells, densely arrayed in Bradford and nearby counties (Pennsylvania), and near 661 pre-existing oil and gas wells. The majority of these, 92%, were unconventional wells, drilled with horizontal legs and hydraulically fractured. Our data set is hundreds of times larger than data sets used in prior studies. In contrast to prior findings, we found no statistically significant relationship between dissolved methane concentrations in groundwater from domestic water wells and proximity to pre-existing oil or gas wells. Previous analyses used small sample sets compared to the population of domestic wells available, which may explain the difference in prior findings compared to ours.

An evaluation of the ability of chemical measurements to predict polycyclic aromatic hydrocarbon‐contaminated sediment toxicity to Hyalella azteca

The present study examined the ability of three chemical estimation methods to predict toxicity and nontoxicity of polycyclic aromatic hydrocarbon (PAH) -contaminated sediment to the freshwater benthic amphipod Hyalella azteca for 192 sediment samples from 12 field sites. The first method used bulk sediment concentrations of 34 PAH compounds (PAH34), and fraction of total organic carbon, coupled with equilibrium partitioning theory to predict pore-water concentrations (KOC method). The second method used bulk sediment PAH34 concentrations and the fraction of anthropogenic (black carbon) and natural organic carbon coupled with literature-based black carbon-water and organic carbon-water partition coefficients to estimate pore-water concentrations (KOCKBC method). The final method directly measured pore-water concentrations (pore-water method). The U.S. Environmental Protection Agencys hydrocarbon narcosis model was used to predict sediment toxicity for all three methods using the modeled or measured pore-water concentration as input. The KOC method was unable to predict nontoxicity (83% of nontoxic samples were predicted to be toxic). The KOCKBC method was not able to predict toxicity (57% of toxic samples were predicted to be nontoxic) and, therefore, was not protective of the environment. The pore-water method was able to predict toxicity (correctly predicted 100% of the toxic samples were toxic) and nontoxicity (correctly predicted 71% of the nontoxic samples were nontoxic). This analysis clearly shows that direct pore-water measurement is the most accurate chemical method currently available to estimate PAH-contaminated sediment toxicity to H. azteca.

Can the HGM classification of small, non-peat forming wetlands distinguish wetlands from surface water geochemistry?

We report the results of a detailed 12-month study of 23 freshwater wetlands and one larger synoptic characterization of 55 freshwater wetlands to test whether a hydrogeomorphic (HGM) classification of the wetlands into lotic (attached to streams) and terrene (groundwater fed) classes meaningfully discriminated wetland surface water chemical composition in the mountainous Catskill-Delaware watersheds of southeastern New York State. Most of these hillslope wetlands are underlain by thin, largely siliceous mineral soils and have minimal peat cover. Nonparametric one-way ANOVA (Kruskal-Wallis) tests based on measurements of SC, Ca2+, Mg2+, Na+, DOC, TDN, TDS, Si, SO42−, pH, DO, K+, Cl−, NH4+, NO3−, TDP, and HCO3− failed to reject the null hypothesis that the surface water chemistry of lotie and terrene wetlands was identical. Results of the statistical tests showed that the only significantly different chemical species in surface waters from the two HGM landscape classifications were SC, Na+, and Cl−, which was clearly related to individual wetland proximity to road salt additions. Isotopic analyses of 2H and 18O for 30 synoptic wetland surface waters also failed to demonstrate significant differences for any of the HGM wetland classes. Based on the results of these data, we caution that landscape position, landform, water flow path, and water body type may not be accurate in making wetland classifications for HGM assessment in all locations. Underlying geology should be considered before making assumptions that water chemistry will differ by landscape position, and wetland functions dependent on water chemistry should be evaluated accordingly.

Background concentrations of PAHs and metals in surface and subsurface soils collected throughout Manhattan, New York

ABSTRACT This article summarizes the results from a survey of polycyclic aromatic hydrocarbon (PAH) and metal concentrations measured in surface and subsurface soil samples that were collected from background locations throughout Manhattan, New York, between August 2005 and May 2006. The 95th percentile total 16 US EPA Priority Pollutant PAH concentrations in surface and subsurface soils were 24.8 and 53.1 mg/kg, respectively. Diagnostic PAH source ratios for surface and subsurface soils are presented, which provide plausible bounds for where these ratios would and would not be able to confidently differentiate background soils from soil samples that are impacted by PAH contamination. The 95th percentile concentrations for lead in surface and subsurface soils were 891 and 2,540 mg/kg, respectively, and the 95th percentile concentrations for mercury in surface and subsurface soils were 1.9 and 2.7 mg/kg, respectively. A not-unexpected finding of the study was that most surface soils and all subsurface soils contained a relatively high fraction of anthropogenic carbon, in addition to the presence of historic fill materials such as glass, brick, coal, and slag from more than 400 years of human activity on Manhattan Island. The concentration ranges for PAHs and metals measured in these background soil samples, coupled with the visual observations of historic fill materials in nearly all soil samples, emphasize that soils in Manhattan are altogether different from rural soils and thus warrant a different framework for site management decisions than rural soils.

Predicting toxicity to Hyalella azteca in pyrogenic-impacted sediments-Do we need to analyze for all 34 PAHs?

Polycyclic aromatic hydrocarbons (PAHs) are major drivers of risk at many urban and/or industrialized sediment sites. The US Environmental Protection Agency (USEPA) currently recommends using measurements of 18 parent + 16 groups of alkylated PAHs (PAH-34) to assess the potential for sediment-bound PAHs to impact benthic organisms at these sites. ASTM Method D7363-13 was developed to directly measure low-level sediment porewater PAH concentrations. These concentrations are then compared to ambient water criteria (final chronic values [FCVs]) to assess the potential for impact to benthic organisms. The interlaboratory validation study that was used to finalize ASTM D7363-13 was developed using 24 of the 2-, 3-, and 4-ring PAHs (PAH-24) that are included in the USEPA PAH-34 analyte list. However, it is the responsibility of the user of ASTM Method D7363 to establish a test method to quantify the remaining 10 higher molecular weight PAHs that make up PAH-34. These higher molecular weight PAHs exhibit extremely low saturation solubilities that make their detection difficult in porewater, which has proven difficult to implement in a contract laboratory setting. As a result, commercial laboratories are hesitant to conduct the method on the entire PAH-34 analyte list. This article presents a statistical comparison of the ability of the PAH-24 and PAH-34 porewater results to predict survival of the freshwater amphipod Hyalella azteca, using the original 269 sediment samples used to gain ASTM D7363 Method approval. The statistical analysis shows that the PAH-24 are statistically indistinguishable from the PAH-34 for predicting toxicity. These results indicate that the analysis of freely dissolved porewater PAH-24 is sufficient for making risk-based decisions based on benthic invertebrate toxicity (survival and growth). This reduced target analyte list should result in a cost-saving for stakeholders and broader implementation of the method at PAH-impacted sediment sites. Integr Environ Assess Manag 2016;12:493-499.

A Statistical Evaluation of Sediment Quality Triad Benthic Community Measurements in PAH-Impacted Sediments at a Manufactured Gas Plant Site along the Hudson River

The sediment quality triad (SQT) assumes that three measurements (sediment chemistry, laboratory bioassay, and benthic macroinvertebrate counts) comprise an independent assessment of impact, which when integrated using a weight-of-evidence approach provides a comprehensive assessment of risk. An SQT assessment was conducted on 41 sediment samples collected adjacent to a manufactured gas plant site on the freshwater reach of the Hudson River in New York State. The assessment shows that the benthic macroinvertebrate data did not correlate with either sediment or pore water polycyclic aromatic hydrocarbon (PAH) concentrations, nor did these data show consistent relationships to the results of laboratory bioassay testing (Hyalella azteca 28-day survival or biomass). The benthic community across the site and reference areas was comprised of few taxa, all of which were pollution-tolerant organisms with tolerance values greater than or equal to five. Only in significantly impacted sediment samples with PAH concentrations in the thousands of milligrams per kilogram, pore water concentrations above 100 toxic units, and visible non-aqueous phase liquid present in the sample did the benthic macroinvertebrate data show a response. In contrast, sediment and pore water PAH measurements and H. azteca toxicity testing provided consistent interpretation of impact. These results illustrate that benthic macroinvertebrate data may contain less information value and be a more challenging line of evidence to interpret in triad studies conducted in certain ecological settings; in this case, a large-order river with a relatively depauperate benthic community dominated by species tolerant of PAHs.

Volatile Organic Compounds from Coal Tar and Soil Vapor Samples at MGP Sites

This study characterized organic compounds found in New York State manufactured gas plant (MGP) coal tar vapors using controlled laboratory experiments from four separate MGP sites. In addition, a limited number of deep (0.3–1.2 m above coal tar) and shallow (1.2–2.4 m above coal tar) soil vapor samples were collected above the in situ coal tar source at three of these sites. A total of 29 compounds were consistently detected in the laboratory-generated coal tar vapors at 50°C, whereas 24 compounds were detected at 10°C. The compounds detected in the field sample results were inconsistent with the compounds found in the laboratory-generated samples. Concentrations of compounds in the shallow soil vapor sample were either non-detectable or substantially lower than those found in deeper samples, suggesting attenuation in the vadose zone. Laboratory-generated data at 50°C compared the (% non-aromatic)/(% aromatic) ratio and indicated that this ratio may provide good discrimination between coal tar vapor and common petroleum distillates.