Work on Water and Sediment Quality in the San Juan River (NM, UT)

During a recent, high profile, chemical waste spill I analyzed daily surface water and sediment samples in the San Juan River for total metals.  I coordinated my work with multiple State and Tribal agencies and EPA headquarters.  I established historical background concentrations which served as benchmarks throughout the event.  Sediment contamination mapping was aided using hydrometrological information for the river system.

san-juan-sediment-analysis_9-15-15

san-juan-river-sw-analysis

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Work on the Refugio Oil Spill

This is a presentation about use of fluorometry to detect dispersed and dissolved oil.  Work was conducted in May 2015 at the Refugio Pipeline Incident, Santa Barbara, CA.

fluorometer-refugio

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SETAC Poster – investigation of plastics in sediment at the Tijuana Estuary

Here’s my poster from SETAC 2016.

hla-setac-poster-tijuana-estuary-plastic-pollution-ver-2

 

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Thoughts on Marine Debris Research Needs

Environmental remediation practitioners must assess the fate and extent of plastic garbage in marine environment. There is a an extremely vast gap in understanding where plastic debris is found, how it behaves in the ocean, and what impacts it has on aquatic ecosystems including very likely impacts to human food resources and human health outcomes.

We must endeavor to understand how marine plastic, first by its presence and by its sources and sinks, threatens ecological and economic resources. Is any part of the ocean resilient in the face of threatening and unceasing tides of plastic garbage? To understand the extent and movement of marine plastic debris, technology must be developed and refined to detect plastic debris in the ocean and tag and track it to understand its behavior and its adverse environmental impacts. While numerous studies show wide variation in plastic content in surface net trawls, a perhaps exponentially larger fraction is undetected by these conventional approaches, leaving more questions than answers. Micro plastics likely pose the greatest harm and yet at present no attempt has been made to quantify these fractions of this endless stream of garbage.

Beyond the known and yet unknown physical damages resulting from plastic contamination, plastic debris also acts as a vector for POP uptake to aquatic organisms and may have a role in contaminant fate and transport in aquatic food webs. Plastic uptake has been observed in connection with excess POP loading in fish tissue. Key food chain species are known to suffer toxic effects of contact with micro plastic particles.

To get at these questions, we must assess issues such as the role of plastic type, photo-disintegration, particle size distribution in the various marine matrices, buoyancy, and other surface and subsurface dispersion (e.g., water column, shoreline, benthic sediments).  Particular focus must be paid to the smallest, highest surface area, particles with the highest incidence of ingestion, as these may well contribute contaminants into food webs.

Research Impact on Clean Water Policy
Research and extent and impacts of plastic debris will shed light on policy short comings. When considering stormwater, non-point source, pollution policy and regulation, Federal and State authorities lack the information required on plastic fate and extent, to make informed decisions. Measuring debris quantity and other properties, while holding waste generation per capita as a constant, might highlight large differences between coastal cities pointing to their stormwater and even solid waste management strategies as possible culprits. Plastic types and even brands are important to understanding upstream sources. Data on these elements will provide information to target waste management and minimization approaches.

Likewise, plastics posing significantly greater environmental fugacity, the likelihood of distant transport of breakdown products with marine reactive qualities, could be replaced with more suitable formulations. Plastics with decreased propensity for photo-disintegration and low contaminant ad/absorption rates (Kd) may be less harmful in the aquatic environment and may be better managed on-land (recycled?) compared to highly reactive plastic formulations subject to escape disintegration and ingestion.

Research Impact on Environmental Restoration Objectives
Plastic toxicity in the environment is of great concern.  Efforts to understand plastic toxicity will include investigation of both toxic contaminants such as POPs (e.g., PCBs) and toxic plastic components or plasticizers (e.g., BDEs), but also physical location (deposition and plume migration), likelihood of aquatic organism exposure, impacts on resources at risk, and potential risk from plasticizer chemical and POP uptake.  These all have confounding effects on aquatic restoration objectives.

From Superfund to Natural Resource Damage Assessment to Endangered Species Critical Habitat and Clean Water Act Restoration needs, these issue confound high dollar cleanups and interventions often required by law and by regulators. The outcomes of these actions and policies, when confounded by the emerging role of plastic debris, may mask measurement of environmental benefit. It is imperative that we act now to take the lead in addressing the uncertainty of the impact of marine plastic debris on large risk-based cleanup decisions.

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Environmental Analysis Snapshot

In the environmental remediation business pretty much all the methods are in the”SW-846,” our manual of test methods.  If you look at the Table of Contents at: http://www.epa.gov/wastes/hazard/testmethods/sw846/pdfs/toc.pdf you’ll see them all listed and I’ll mention a couple here that we work with.
What’s not in there is what we do in the field for monitoring.  We’re still using PID/FID instruments and radiation meters, NaI scintillation, for most initial characterizations.  We also have an instrument that using atomic absorption to analyze mercury vapor and we’ve developed situation specific air sampling and analysis method selection guides which I think are excellent.  For field screening, we often use X-ray fluorescence instrumentation (6200) for metal detection and immunoassay (4000 series) for pesticide detection and we correlate these results to lab analyses routinely.
In water and in air we use GCMS for VOCs (8260) and SVOCs (8270), but we use the soil methods for VOCs only rarely.  Nowadays we are using SUMMA canisters (TO-14) for air sampling although we still use TO-15 with sorbent tubes periodically.  We would use “SUMMAs” for most things from indoor air sampling up through a disaster like the Chevron Fire with the Air Quality Management District as an example.  For pesticides, 99% of the time we deal with the organochlorines, not the organophosphates, in soils and sediments – usually at pesticide dumpsites although rumors are that OPs are resurfacing in CA.  We use GCMS (8081) with Soxhlet extraction for these pesticide analyses.  We deal with PCBs a lot in soil, sediment and oil (8082), and PAHs mostly at oil spills (8100).  In recent work on fish tissue we’ve been doing high resolution GCMS for PCBs and pesticides and some plasticizers (Alkylphenol, PBDE and BPA).
Metals are also very common for us to work with, lead and arsenic in particular in soils.  Pretty sure we use 6010 – ICP Atomic Emission with acid digestion (3050).  Sometimes we do inorganic mercury as well.  Rarely we do the total and dissolved methods for surface waters.  We’ve been working on lead and arsenic bioavailability methods lately as well.   Finally, we do Radium in soils and in water (as well and U and gross alpha/beta – in water).  Radium in soils has been a weird deal and we vacillate between gamma spectroscopy and radon emanation methods.  We do this for Uranium mine cleanup but we still have not decided on the preferred method.
PM 2.5 monitoring is becoming very important,  and the E-BAM (from MetOne, Inc.) is a great real-time tool for this. Colleagues at the Air Resources Board routinely deploy portable E-BAMs at large wildfires adding to the State-wide, fixed monitoring network.

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Special Hazards of Oil Spills from Sunken Wrecks

Sunken tug, loaded with oil containing sediments with moderately sized oil tankage

Sunken tug with moderately sized oil tankage, sheening common at low-tide

Sunken wrecks containing fuel oils pose significant environmental and human health threats

Recent research and lines of evidence suggest that oil in submerged wrecks poses a greater toxic threat, once liberated, compared to background pollution in urban waterways like San Francisco Bay.  Despite myriad other pollutant inputs in an urban environment like the Bay, liberated oil from makes a difference, locally, to human health and the aquatic environment.

Following the M/V Cosco Busan incident in 2007, acute toxicity of the spilled oil (Bunker C: Intermediate Fuel Oil) was observed based on evidence of sublethal cardiac effects (i.e., arrhythmia, edema) in herring embryos incubated near oiled shorelines. Significant increases in bradycardia and pericardial edema were observed in caged embryos from oiled sites relative to nonoiled locations.  Further, natural spawn from oiled intertidal zones demonstrated tissue necrosis and high rates of morphological abnormalities and lethality when exposed to spilled oil in San Francisco Bay compared to non-spill impacted areas.  Researchers demonstrated that this toxicity was due to the Poly Aromatic Hydrocarbon (PAH) fraction of the oil and its environmental fate (Incardona et al. 2012 in The Proceedings of the National Academies of Sciences).

Appreciable concentrations of PAHs are present in residual fuels because of the common practice of using both uncracked and cracked residues in their manufacture. The following table lists the concentrations of three- to five-ring aromatics determined in one sample of No. 6 fuel oil:

Expected Concentration of known PAHs in No. 6 Fuel Oil in ppm  (Phototoxicity Class: H,M,L)
Phenanthrene – 482 ppm (L) Chrysene – 196 ppm (M – NOAA SQuiRT 0.3 ppm)
2-Methylphenanthrene – 828 ppm Triphenylene – 31 ppm (L)
1-Methylphenanthrene – 43 ppm Benzo(a)pyrene – 44 ppm (H – SQuiRT 0.3 ppm)
Fluoranthene – 240 ppm (H) Benzo(e)pyrene – 10 ppm (H)
Pyrene – 23 ppm (H – NOAA SQuiRT 0.3 ppm) Perylene – 22 ppm (H)
Benz(a)anthracene – 90 ppm (SQuiRT 0.3 ppm) (H) Octanol/Water Log: 3.3 to 7.06

(from Irwin et al. 1997)

Significant amounts of fuel oil have been identified in the “Respect” by EPA contract divers including fuel tanks (as much as 500 gallons total storage), oil sheen in the ship compartments, and heavily oiled sediments on board and ultimately in EPA’s land-based sediment settling tank system.  Fuel oil in the “Respect” is likely to be similar in original chemical makeup (also in part, Bunker C) to the M/V Cosco Busan’s fuel oil.  The Respect sank in the same year as the M/V Cosco Busan spill, also in the San Francisco Bay.

In the hull of a submerged wreck such as the “Respect”, Bunker C fuel oil is likely to be subject to anaerobic, bacterially mitigated, processes.  Anaerobic substitution reactions, for example with sulfur compounds could increase concentrations of toxic PAHs in the oil mixture.  These reactions within the submerged oil result in a multitude of toxic PAHs in the oil mixture (e.g., dibenzothiophenes which may demonstrate Microtox toxicity).  These reactions also change the physical properties of the oil perhaps increasing solubility of oil fractions.  Conversely typical “weathering” from solublization, hydrolysis, and evaporation, commonly observed and understood from surface oil spills is likely not to occur. 

Many PAHs are phototoxic (or activated in sunlight) and phytotoxic

Illegal mooring atop sunken wreck

Illegal mooring atop a sunken wreck

Many PAHs are known human carcinogens over chronic, long duration exposures.  Following a small, or periodic, oil release in Oakland Estuary, a common boating and fishing area, short term exposures could result in dermatitis, erythema and skin burns as well as eye irritation.  These are symptoms are exacerbated by sunlight and may be pre-cancerous (ATSDR 2009).  Similarly food species may become contaminated locally by the PAH fraction of spilled oil (Klasing 2013).

PAHs are phototoxic and concentrations have been shown in shallow tidal areas of San Francisco Bay, co-located with impacted herring (Incardona et al. 2012).  Aquatic toxic effects similar to the herring exposures may be realized by State and Federal Endangered and Threatened fish species such as the Green Sturgeon and Salmon, especially in juveniles as these species are found in the Oakland Estuary and environs. 

Almeda et al. also demonstrated that UV radiation plays an important role in the toxicity of crude oil aquatic life.  UV radiation may increase the toxicity of spilled oil by 2- to 50,000-fold due to the photosensitization and/or photomodification of the PAH fraction.  These processes impose toxic stress to zooplankton in particular due to the fact that these organisms are translucent/transparent and frequently live in the upper water column where elevated UV radiation is present (Almeda et al. 2013).  Similarly PAHs threaten the health of Essential Fish Habitat, especially sub-tidal Eel grass beds, within the central San Francisco and San Leandro Bays.   

References

Almeda, Rodrigo et al. 2013. Effects of Crude Oil Exposure on Bioaccumulation of Polycycl

Wreck - aground in San Leandro Bay

Wreck – aground in San Leandro Bay

ic Aromatic Hydrocarbons and Survival of Adult and Larval Stages of Gelatinous Zooplankton. PLoS ONE 8(10): e74476. doi:10.1371/journal.pone.0074476.

Incardona, John et al. 2012.  Unexpectedly high mortality in Pacific herring embryos exposed to the 2007 Cosco Busan oil spill in San Francisco Bay.  Proceedings of the National Academy of Sciences.

Irwin, Roy  et al. 1997.  Environmental Contaminants Encyclopedia Fuel Oil Number 6Entry.  National Park Service.

Klasing, Susan et al. 2013. Protocol for Risk Assessment to Support Fisheries Re-opening Decisions for Marine Oil Spills in California.  Office of Environmental Health Hazard Assessment, California Environmental Protection Agency.

Prepared by Harry L. Allen, MS and Harry Allen Ph.D.; Photos by Todd Thalhamer

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November 28, 2013 · 7:02 am

Toxaphene Degrades!

Former Toxaphene dip-vat

Former Toxaphene dip-vat

My team and I will begin remediating soils at the South Fork Te-Moak Indian Reservation near Elko, NV this Spring.  Based on experience with similar Toxaphene-contaminated sites, we’ve selected ex-situ bioremediation as the treatment technology best suited to achieving Site cleanup goals.At previous sites of this type, we’ve constructed lined and covered cells (referred to as “burritos”) filled with a mixture of contaminated soil, water, and nutrients to promote the anaerobic biodegradation of Toxaphene. The winning nutrient “recipe” thus far includes 0.50 percent (by weight) blood meal, 0.50 percent (by weight) phosphates (9 parts disodium phosphate to 1 part monosodium phosphate), and 0.40 percent (by weight) starch, so that 1.4 percent of the total solid mixture (by weight) consists of amendments.

To test applicability at South Fork, I recently conducted a bench-scale test.  For this I mixed approximately 80g of contaminated soils with 0.50% commercial blood meal nutrient and some Royal brand rice for starch.  The mixtures were prepared in 1-liter nalgene-brand sample bottles.  The test bottle was then flooded while the control was left dry – both were sealed and submerged.  The test flasks were left for 9 weeks and were sampled on December 28, 2012.  Two-samples were sent to the EPA Region 9 laboratory for Pesticide analysis after a 1:1 Acetone/Hexane extraction.

Metlar balance containing sample container.

Results demonstrated a 54% reduction in Toxaphene concentration from 61,000 ppb to 28,000 ppb as well as a reduction in Chlordane concentration, thought to be a recalcitrant “biomarker”.  This crude test demonstrated that indigenous bacteria in the South Fork Site soil can degrade Toxaphene and therefore supports this treatment approach for the Site.The treatment cells we construct are designed to maximize the potential for anaerobic bacteria to degrade toxaphene. The cells are lined with visqueen in order to prevent water loss and promote anaerobic conditions. Cell contents are homogenized during several phases of the cell construction process to distribute Toxaphene contamination and nutrients as evenly as possible.Excavated soil will be run through a sieve to remove rocks and debris. Nutrients will be added to the soil and mixed in a bin, slightly moistened, and moved to the treatment cells. Water will be added to the treatment cells as they were filled with the amended soil mixture.  Finally the cells will be sealed with visqueen and sampling ports with gas release valves will be installed around the perimeter of each cell.  We should be able to collect samples periodically to demonstrate reductions in Toxaphene concentrations.

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