Estimating PAH sources in harbor sediments using diagnostic ratios

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the global environment and are subsequently transported into aquatic sediments. As PAHs are formed by various processes, source identification using diagnostic ratios can provide insight to PAH emission sources to distinguish between pyrogenic and petrogenic PAH sources. PAH diagnostic ratios were applied as a forensic source apportionment technique to assess aggregate historical sediment data from 31 small craft harbors (SCHs) across Nova Scotia, Canada. Multiple diagnostic ratios suggest that PAHs present in Nova Scotia SCH sediments are pyrogenic (combustion) in origin, while consistently suggesting that coal‐related PAH sources are potential dominant specific sources. National Institute of Standards and Technology Standard Reference Materials (SRMs) were used as reference for coal tar, urban dust, and diesel exhaust particulates in ratio applications. The SRM for coal tar was most similar to Nova Scotia SCH sediments in multiple ratio applications. Diagnostic ratio results were corroborated by comparing the PAH profile of sediments to source profiles from the literature. Results indicate that Nova Scotia SCH sediments follow global trends by exhibiting a dominant pyrogenic PAH signature, and the specific coal‐related PAH signature of Nova Scotia SCH sediments may be influenced by contamination inputs related to historical industrial coal mining and combustion activities in the province.     

Groundwater Impacts on Surface Water and Sediment—Gowanus Canal,Brooklyn, New York

The Gowanus Canal Superfund Site in Brooklyn, New York, is an approximately 1.5‐mile (1.61‐km) long estuary that was historically converted into a canal for industrial and commercial purposes. Three manufactured gas plants (MGPs) were formerly located on the Gowanus Canal and discharged waste into it. Surface sediments remain highly contaminated with polycyclic aromatic hydrocarbons (PAHs) long after the MGPs were razed. A hydrogeologic assessment indicates that groundwater passes through the deeper coal tar–contaminated sediment prior to discharging to the canal. This study was undertaken to investigate if groundwater passing through coal tar–contaminated sediment could be responsible for the ongoing contamination of both surface sediments and surface water in the canal. PAH compound distributions in surface water samples collected from the tidal canal at low tide were compared with PAH compounds found in adjacent groundwater‐monitoring wells, point sources (combined sewer overflows [CSOs]), and surface sediments. The results indicate a strong correlation between PAH contaminant distributions in groundwater, sediment, and surface water, indicating that contaminated groundwater passing through the deeper coal tar–contaminated sediments is the primary mechanism contributing to the contamination of both surface sediment and surface water in the canal. Therefore, any sediment remediation efforts in the Gowanus Canal that fail to evaluate and control the upward transport processes have a high chance of failure due to recontamination from below.  ©2016 Wiley Periodicals, Inc.     

Contributions of common sources of polycyclic aromatic hydrocarbons to soil contamination

Asphalt products, particularly sealants, are prepared using petroleum products that contain a com‐plex mixture of aliphatic and aromatic hydrocarbons, including polycyclic aromatic hydrocarbons (PAHs). Clearly, these products are ubiquitous in urban environments, which raises an issue regard‐ing the potential for PAHs to be transported from parking lots to underlying or adjacent soil, surface‐water bodies, or groundwater. Based on a literature review, there are limited studies focus‐ing on this issue; however, the studies that have been published have fascinating conclusions. The literature shows, as expected, that asphalt‐based products contain PAHs. The highest PAH concen‐trations are present in asphalt sealants, particularly those manufactured using coal tar. Furthermore, due to the low solubility and high partition coefficients of PAHs, the potential for PAHs to leach from asphalt surfaces is negligible, which has been confirmed by leachability studies. Thus, there is little risk that PAHs will be present in stormwater runoff or leach into groundwater from asphalt‐paved areas in a dissolved form. However, asphalt pavement and sealants produce particulate matter that can contain concentrations of PAHs in the sub‐percent range (100s to 1,000s mg/kg total PAHs) that is transported in stormwater runoff. Some studies show that this can cause soil and sediment con‐tamination with total PAH concentrations in the range of 1 to 10 mg/kg. From a remediation per‐spective, many site cleanups are conducted to remediate the presence of PAHs to cleanup goals below 1 mg/kg or, in some cases, 0.1 mg/kg or lower. From a total risk perspective, remediating sites to low PAH cleanup goals may be unwarranted in light of the risk of transportable PAHs produced from paved parking surfaces. In other words, is it reasonable to conduct a cleanup to remediate low PAH concentrations and then redevelop the area with asphalt pavement and sealant, which may pose a greater PAH‐related risk? © 2006 Wiley Periodicals, Inc.     

Progress toward remediation of the Sydney Tar Ponds: A major Canadian PCB/PAH “superfund” site

The Muggah Creek estuary in Sydney, Nova Scotia, received liquid and solid wastes from a steel mill and its associated coke ovens for approximately 100 years. This resulted in pollution of soils and sediments with polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), heavy metals, and other pollutants, including those in untreated domestic wastewaters. The Canadian federal and Nova Scotia provincial governments organized the Sydney Tar Ponds Agency (STPA) to develop a remediation approach for the Coke Ovens site soils and Sydney Tar Ponds sediments. The STPA developed a remediation approach for the Sydney Tar Ponds sediments, involving solidification/stabilization (S/S) through mixing cement and other materials into the sediments, and then capping them as a waste pile. High‐density polyethylene (HDPE) plastic sheeting vertical barriers are proposed to be used to divert groundwater and surface water from entering into the S/S‐treated sediments and to collect any water and associated pollutants released from the S/S‐treated sediments. The Coke Ovens site soils are proposed to be landfarmed to reduce some of the PAHs and other pollutants and then capped with a layer of soil. This remediation program is estimated to cost on the order of $400 million (CAN). This article presents a review of the significant potential problems with the STPA proposed remediation strategy of the Sydney Tar Ponds sediments and Coke Ovens site soils. © 2006 Wiley Periodicals, Inc.     

Demonstrating Contaminant Degradation at an MGP Site With Metabolic Gas Flux and Radio Carbon Dating

Obtaining lines of evidence indicating that contamination in sediment environments is degrading and being transformed to less toxic forms is an important component of building support for a monitored natural recovery remedy for contaminated sediments. This project was a field demonstration of manufactured gas plant contaminant degradation in river sediments using metabolic gas flux and was performed in an urban area section of a river in northeastern Indiana. CO₂ sorbent traps were deployed to measure CO₂ flux from the river sediments. Sediment samples were collected and analyzed for polycyclic aromatic hydrocarbon (PAH) concentrations and for microbial community composition using molecular techniques. The results showed that the deployment was successful, measuring CO₂ flux at all sediment locations and demonstrating that microbial contaminant degrading activity was occurring in the sediments. Radio carbon dating showed a significant portion of the CO₂ being generated (approximately 19–27 percent) was the result of fossil fuel degradation. Molecular results showed that the microbial community consisted of phylotypes known to be associated with monocyclic aromatic and PAH degradation. ©2017 Wiley Periodicals, Inc.     

Sedimentary Record of Polycyclic Aromatic Hydrocarbons in the Gulf of Trieste (Northern Adriatic Sea)

To reconstruct a history of polycyclic aromatic hydrocarbon (PAH) pollution in the Gulf of Trieste, one of the largest urbanized areas in the Adriatic Sea, we analyzed three long sediment cores collected between 1996 and 1997. Concentrations of total PAHs, the sum of 16 PAH compounds and six of their methylated analogues, in all three cores show a decrease from 600–800 ng g⁻¹, at the surface, to levels below 250 ng g⁻¹ in deepest layers (down to 3 m). The same trend was shown with separate representative pyrogenic PAHs (pyrene, benzofluoranthene and phenanthrene). Using Hg as a recent geochronological tracer, we observe an increasing input of PAHs since the beginning of the 20th Century and, especially, after the Second World War coinciding with increasing industrialization and urbanization of the region. This correlation is supported by PAH ratios that are indication of combustion processes and represent a marker for anthropogenic inputs. No correlation exists between PAHs and black carbon within the core profiles, indicating two different fractions of the ‘black carbon continuum’.     

Measurements of PCB Fluxes into the Atmosphere from a Site Receiving Stabilized Dredged Material

A 50 ha known contaminated site in Bayonne, New Jersey, U.S.A. is permitted to receive up to 3 × 10⁶ m³ of sediment dredged from navigation channels in the New York/New Jersey Harbor. Much of the sediment is expected to contain low to moderate concentrations of industrial and agricultural chemicals, including Polychlorinated Biphenyls (PCBs). The dredged material brought to the site is stabilized with cement and then placed as a capping and grading layer. The flux of PCBs from drying stabilized dredged material has been estimated from measurements of PCB air concentrations at two heights above the ground along with micrometeorological observations. A statistically significant gradient in PCB concentrations has been consistently measured in the first 3 m above the ground. Observed PCB fluxes were highest over freshly placed stabilized dredged sediment and decreased as it cured. The highest flux observed in this study was 7214 ng/m²/h, but during subsequent sampling intervals at the same site, the flux estimates decreased by an order of magnitude over a 5-day interval.     

Current status and challenges of remediating petroleum‐derived PAHs in soils: Nigeria as a case study for developing countries

Polycyclic aromatic hydrocarbons (PAHs) are among the world's most significant environmental organic contaminants because of their carcinogenic properties. PAHs are widely distributed globally as a result of releases from numerous natural and anthropogenic activities. Consequently, several PAH monitoring studies have been conducted and remediation approaches explored. This article aims to provide the current status of PAH distribution in Nigeria's oil and gas industrial region in relation to the technologies adopted for PAH remediation. Ideally, the findings will provide insight into the challenges in managing organic contaminants derived from petroleum exploration activities in developing countries with Nigeria as a case study.     

Contaminated land clean-up using composted wastes and impacts of VOCs on land

This paper describes experiments that demonstrate the effects and potential for remediation of a former steelworks site in Wales polluted with polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs). Under field conditions, PAH-contaminated soil was composted in-vessel, with or without organic feedstocks, receiving forced aeration for 80 days followed by 4 months maturation. Treatments compared PAH removal in contaminated soil to contaminated soil mixed with three different organic waste mixes after composting and after composts were spread to land. After composting, PAH concentrations declined in all treatments, by up to 38%. Sixteen months after the composts were landspread and vegetation was established, only those containing contaminated soil with organic additions exhibited further PAH removal, by up to 29%. Composting resulted in a decline in the relative concentration of small PAHs, whereas the landspreading-vegetation phase saw a decline in the relative concentration of medium PAHs in two of the three composts exhibiting PAH removal. Under controlled glasshouse conditions, vegetated soil columns of differing depths were exposed to VOCs from beneath. VOC vapour affected both shoot and root growth and soil microbial activity; effects varied with distance from the VOC source. This work demonstrated that on-site remediation of aged PAH-contaminated land can be successfully initiated by in-vessel co-composting followed by land spreading and vegetation, within a practical timeframe.     

Active capping technology—New approaches for in situ remediation of contaminated sediments

This study evaluated pilot‐scale active caps composed of apatite, organoclay, biopolymers, and sand for the remediation of metal‐contaminated sediments. The active caps were constructed in Steel Creek, at the Savannah River Site near Aiken, South Carolina. Monitoring was conducted for 12 months. Effectiveness of the caps was based on an evaluation of contaminant bioavailability, resistance to erosion, and impacts on benthic organisms. Active caps lowered metal bioavailability in the sediment during the one‐year test period. Biopolymers reduced sediment suspension during cap construction, increased the pool of carbon, and lowered the release of metals. This field validation showed that active caps can effectively treat contaminants by changing their speciation, and that caps can be constructed to include more than one type of amendment to achieve multiple goals. © 2012 Wiley Periodicals, Inc.     

Assessment of Heavy Metal and PAH Contamination of Urban Streambed Sediments on Macroinvertebrates

The results from measuring PAH and metal contamination together with macroinvertebrate communities at 62 headwater stream sites gives a significant insight into the range and scale of contamination. Monitoring streambed sediments at 62 sites from rural to inner city and in industrial locations presented a unique opportunity to distinguish the conditions that enhance pollution runoff at sites that are less obviously `at risk' and to compare these results with sites of expected high contamination, for example in industrial areas and at motorway junctions. We used pCCA (partial Canonical Correspondence Analysis) to tease out the relationships between individual macroinvertebrate families and specific metal and PAH contaminants, and showed that it is not always the metals and PAHs with the greatest total concentrations that are doing the damage to the ecology. Ni and Zn are the critical metals, while benzo(b)fluoranthene, anthracene and fluoranthene are the most contaminating PAHs. The results identify previously unrecognized `high risk' pollution sources, lay byes used for commercial parking, on-street residential parking areas, and the junctions at the bottom of hills with traffic lights, where surface runoff feeds rapidly to the streams. While this study looks at sites across Yorkshire, UK, it clearly has a broader significance for understanding contamination risks from diffuse runoff as a prerequisite for effective sustainable urban drainage system (SUDS) agendas and the protection of urban stream ecology.     

Managing bioremediation of a creosote‐contaminated superfund site by optimizing moisture and temperature in a biopile

Soil moisture content and temperature in a contaminated soil biopile equipped with immobilized microbe bioreactors (IMBRs) were optimized during ex situ bioremediation at a creosote‐contaminated Superfund site. Efficiency of remediation during warm summer months without soil‐temperature and moisture optimization was compared with that of cold winter months when corrective measures were applied. Significant reduction (35 percent) in total polycyclic aromatic hydrocarbons (PAHs) was observed, compared to 3.97 percent without corrective measures (p < 0.05). Kinetic rates (KRs) for total PAH removal were significantly enhanced from 3.93 to 50.95 mg/kg/day. KRs for removal of high molecular mass four‐to‐six‐ring PAHs were also significantly enhanced from 70.29 mg/kg/day to 97.45 mg/kg/day ( p < 0.05). Bioremediation of two‐ and three‐ring PAHs increased significantly from 15 percent to 40 percent. Benzo[a]pyrene toxicity equivalent mass (BaP_equiv) was significantly reduced by 48 percent with KR of 0.47 mg/kg/day as compared to 22 percent with KR of 0.14 mg/kg/day (p < 0.05). Soil moisture content was enhanced from 15.7 percent to 41.4 percent. © 2007 Wiley Periodicals, Inc.     

Environmental Effects Monitoring in Sydney Harbor During Remediation of One of Canada's Most Polluted Sites: A Review and Lessons Learned

This article reviews a comprehensive marine environmental effects monitoring program (MEEMP) comprised of components capable of detecting changes in the marine environment over short or extended temporal scales during remediation of one of Canada's most polluted sites at the Sydney Tar Ponds. The monitoring components included: water and sediment quality, amphipod toxicity testing, mussel tissue, crab hepatopancreas tissue, and benthic community assessments. The MEEMP was designed to verify the impact predictions for the remediation project (i.e., no immediate damage to the marine ecosystem through remediation activities). Some components were capable of providing conclusive data (e.g., sediment and water quality), while others only yielded data that were inconclusive or difficult to attribute to remediation activities (e.g., intertidal community assessments and amphipod toxicity testing). Components that provided only inconclusive results or were difficult to attribute to remediation activities were discontinued, resulting in substantial cost savings during the project, but without compromising the overall objectives of the program, which was to monitor for potential adverse environmental effects of remediation on the marine environment in Sydney Harbor and to verify environmental effects predictions made in the Environmental Impact Statement for the project. The rationale for discontinuing certain MEEMP components and discussion of conclusive results are incorporated into “lessons learned” for environmental remediation practitioners and regulators working on similar large‐scale multiyear remediation projects. © 2014 Wiley Periodicals, Inc.     

Behavior of PAHs from sewage sludge incinerators in Korea

Although production of sewage sludge increases every year, its proper treatment has only been recently raised as a new issue, as current landfill and ocean dumping arrangements are expected to become increasingly difficult to manage in the future. The Korean Ministry of Environment plans to diversify its processing facilities and expand its processing systems by 2011, with the purpose of processing all sludge produced in Korea. According to this plan, incineration (including incineration of municipal wastes) will process 30% of the entire sewage sludge throughout the country in 2011. This study reviews the characteristics of PAH, which is one of the organic substances found in sewage sludge during the incinerating process. The total amount of PAH produced from sewage sludge incineration was found to be 6.103 mg/kg on average, and investigation performed on 16 PAHs of inlets and outlets of the air control devices at five full-scale incineration facilities showed that concentrations of the PAHs on the inlet and on the outlet ranged from 3.926 to 925.748 microg/m(3) and from 1.153 to 189.449 microg/m(3), respectively. In the case of the incineration facility fed with municipal waste (95%) and sewage sludge (5%), the total of the PAH emissions concentration was higher than that found at the incineration facilities used exclusively to treat sewage. The combustion of waste vinyl and plastics contained in municipal waste fed into the facility might contribute to the high levels of PAHs in the stack gas. However more investigation is needed on the production mechanism of PAHs at different operating conditions of the incineration facilities, such as the types of waste, and other relevant factors.     

Evaluation of white‐rot fungi for the remediation of creosote‐contaminated soil

Application of fungal‐based bioaugmentation was evaluated for the remediation of creosote‐contaminated soil at a wood‐preserving site in West Virginia. Soil at the site contained creosote‐range polycyclic aromatic hydrocarbons (PAHs) at concentrations in some areas that exceed industrial risk‐based levels. Two white‐rot fungi (Pleurotus ostreatus and Irpex lacteus) were evaluated for remediation effectiveness in a two‐month bench‐scale treatability test. Both fungi produced similar results, with up to 67.3 percent degradation of total PAHs in 56 days. Pilot‐scale testing was performed at the site using Pleurotus ostreatus grown on two local substrate mixtures. During the 276‐day field trial, total PAHs were degraded by up to 93.2 percent, with all individual PAHs except one achieving industrial risk‐based concentrations. It was recommended that fungal‐based remediation be applied to all contaminated soil at the site. © 2002 Wiley Periodicals, Inc.     

Characterisation of polycyclic aromatic hydrocarbons in flue gas and residues of a full scale fluidized bed combustor combusting non-hazardous industrial waste

This paper studies the fate of PAHs in full scale incinerators by analysing the concentration of the 16 EPA-PAHs in both the input waste and all the outputs of a full scale Fluidized Bed Combustor (FBC). Of the analysed waste inputs i.e. Waste Water Treatment (WWT) sludge, Refuse Derived Fuel (RDF) and Automotive Shredder Residue (ASR), RDF and ASR were the main PAH sources, with phenanthrene, fluoranthene and pyrene being the most important PAHs. In the flue gas sampled at the stack, naphthalene was the only predominant PAH, indicating that the PAHs in FBC’s combustion gas were newly formed and did not remain from the input waste. Of the other outputs, the boiler and fly ash contained no detectable levels of PAHs, whereas the flue gas cleaning residue contained only low concentrations of naphthalene, probably adsorbed from the flue gas. The PAH fingerprint of the bottom ash corresponded rather well to the PAH fingerprint of the RDF and ASR, indicating that the PAHs in this output, in contrast to the other outputs, were mainly remainders from the PAHs in the waste inputs. A PAH mass balance showed that the total PAH input/output ratio of the FBC ranged from about 100 to about 2600 depending on the waste input composition and the obtained combustion conditions. In all cases, the FBC was clearly a net PAH sink.     

Toxicity and source assignment of polycyclic aromatic hydrocarbons in road dust from urban residential and industrial areas in a typical industrial city in Korea

This study analyzed the toxicity and sources of polycyclic aromatic hydrocarbons (PAHs) in road dust from six representative areas (three urban residential areas and three industrial areas) from a typical industrial city in Korea. The concentrations and the toxicity equivalent concentrations (TEQs) in road dust varied by area, depending on the type of traffic and industrial activities and the PAHs identified. High correlations between the total concentration and the TEQ of PAHs in road dust were found in road dust from both the urban and industrial areas. To identify the sources of PAHs, this study utilized a factor loading method in a principal component analysis, the ratio of PAHs from combustion sources to total PAHs (ΣCOMB to ΣPAH), and bivariate plots of phenanthrene/anthracene (PA/Ant) versus fluoranthene/pyrene (FL/Pyr), and ΣCOMB/ΣPAH versus FL/Pyr in road dust. The identified origin of the PAHs was fuel combustion, including gasoline, diesel, oil, and coal, used in urban and industrial areas.     

PAH removal using soil and sediment washing at a contaminated harbor site

In tests conducted for the Canadian government on sediment from Thunder Bay Harbour, Ontario, the BioGenesis washing process was demonstrated to be effective in remediating contaminated harbor sediments. Removal efficiencies for 16 polyaromatic hydrocarbons (PAHs) in concentrations exceeding 4,000 parts per million averaged 90 to 95 percent in pilot tests. These results are significant because, until now, washing processes have not proven effective in cleaning the small-size particles of silt and clay that make up most underwater sediments. In Thunder Bay, 81 percent of the particles were less than 38 microns (medium silt) in size. The tests on Thunder Bay sediment were conducted under the auspices of the Contaminated Sediment Treatment Technology Program of Environment Canada's Wastewater Technology Centre. Thunder Bay Harbour is one of 43 “areas of concern” identified by the International Joint Commission of Great Lakes Water Quality.     

Threshold amounts of organic carbon needed to initiate reductive dechlorination in groundwater systems

Aquifer sediment and groundwater chemistry data from 15 Department of Defense facilities located throughout the United States were collected and analyzed with the goal of estimating the amount of natural organic carbon needed to initiate reductive dechlorination in groundwater systems. Aquifer sediments were analyzed for hydroxylamine and NaOH‐extractable organic carbon, yielding a probable underestimate of potentially bioavailable organic carbon (PBOC). Aquifer sediments were also analyzed for total organic carbon (TOC) using an elemental combustion analyzer, yielding a probable overestimate of bioavailable carbon. Concentrations of PBOC correlated linearly with TOC with a slope near one. However, concentrations of PBOC were consistently five to ten times lower than TOC. When mean concentrations of dissolved oxygen observed at each site were plotted versus PBOC, it showed that anoxic conditions were initiated at approximately 200 mg/kg of PBOC. Similarly, the accumulation of reductive dechlorination daughter products relative to parent compounds increased at a PBOC concentration of approximately 200 mg/kg. Concentrations of total hydrolysable amino acids (THAA) in sediments also increased at approximately 200 mg/kg, and bioassays showed that sediment CO₂ production correlated positively with THAA. The results of this study provide an estimate for threshold amounts of bioavailable carbon present in aquifer sediments (approximately 200 mg/kg of PBOC; approximately 1,000 to 2,000 mg/kg of TOC) needed to support reductive dechlorination in groundwater systems. © 2012 Wiley Periodicals, Inc.