The 2004 Marsh Creek Creosote Remediation Technology Demonstration Project

ACAPSAI NTJOHN

THE2004MARSHCREEKCREOSOTE REMEDI ATI ONTECHNOLOGY DEMONSTRATI ONPROJECT

The 2004 Marsh Creek Creosote Remediation Technology Demonstration Project

By Craig Silliphant Tony Matthews Tim Vickers April 2005

Acknowledgements The 2004 Marsh Creek Remediation Technology Demonstration Project marks the end of a fiveyear project to identify the extent of creosote contamination in Marsh Creek, and to provide recommendations for its remediation. This initiative has been supported by numerous community partners including The City of Saint John Canada Post Jacques-Whitford Erb Builders DL Remediation Fundy Engineering The New Brunswick Museum University of New Brunswick in Saint John However, the project would never had been a success without the continued financial support of the New Brunswick Department of the Environment and Local Government through their Environmental Trust Fund.

Environment Canada also assisted with financial and in-kind support. Thanks especially to Art Cook for laboratory analyses and advise on techniques and the interpretation of results.

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Table of Contents Introduction A Brief History Stream Characteristics Creosote Contamination Characteristics of Creosote Remediation Methods in Marsh Creek Phytoextraction of PAH’s by Aquatic Plants in Marsh Creek Objectives of the 2004 Marsh creek Remediation Project

4 4 5 6 7 9 11 11

Methods Active Extraction of the Passive Transport Devices Phytoextraction Test for PAH’s in the tissues of aquatic plants in Marsh Creek

12 12 14

Results Active Extraction of creosote from Passive Transport Devices Analysis for PAH in the tissues of Aquatic Plants in Marsh Creek

17 17 19

Discussion Active Extraction of Creosote from Passive Transport Devices PAH in the tissues of Aquatic Plants in Marsh Creek

21 21 21

Appendices Appendix I. Volumes of creosote collected from individual passive recovery devices in Marsh Creek, in 2004.

Appendix II. Concentrations of polycyclic aromatic hydrocarbon (PAH) fractions found in the tissues of aquatic plants occurring in Marsh Creek, Saint John, New Brunswick. Concentrations are given as ng of PAH per g of wet plant tissue.

Appendix III: Map showing the position of the ACAP Saint John’s creosote extraction sites relative to historical railroad lines. The occurrence location of Site 1 (S1) below the railroad bridge is clearly evident.

Appendix IV. The potential effects of some polycyclic aromatic hydrocarbons on human health.

References

24 25

26 27 29

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Introduction The following provides the information necessary to understand why ACAP Saint John has so aggressively sought to identify the extent of creosote contamination in Marsh Creek, as well as the potential health and environmental implications of what has been described as New Brunswick’s most contaminated site. The 2004 Marsh Creek Remediation Technology Demonstration Project is the culmination of five years of dedication by ACAP staff and volunteers working in conjunction with the New Brunswick Department of Environment and Local Government, Environment Canada, the University of New Brunswick (Saint John), New Brunswick Community College, and the City of Saint John. Our collective efforts have resulted in many unexpected discoveries of the history, culture and wildlife that have been (and continue to be) influenced by the creosote contamination in the Marsh Creek watershed.

A Brief History Marsh Creek is an urban watercourse that originates from several tributaries in the eastern region of the City of Saint John, New Brunswick (Figure 1). The creek extends from the Glen Falls region (east Saint John) and empties into Courtney Bay (south Saint John). Originally called Sebaskastaggan by local Native Americans, Marsh Creek was one of five mouths of the Saint John River, which emptied into the Bay of Fundy (Wright 1966). Eventually the connection between the creek and the river was closed and the other three mouths silled-up leaving the single mouth to the Saint John River (Wright 1966).

Marsh Creek was originally settled in 1762 as part of a land grant acquired by John Simonds, a European fur trader who sailed with a group of colonists under the direction of Captain Francis Peabody. Though most of the colonists moved up river, Mr. Simonds settled on the Marsh Creek land and became a pivotal forefather of the City of Saint John. Water levels in Marsh Creek were heavily influenced by the tides of the Bay of Fundy. As such, John Simonds built a large dam, which also served as a bridge, to limit the amount tidal water entering the creek, thereby preventing the marsh from flooding at high tide (Wright 1966). This would be the first of many anthropogenic stresses the creek’s ecosystem would be subjected to. The rise of considerable farming activities along the banks and lowlands of Marsh Creek eventually gave way to the development pressures of commercial and industrial operations. Inevitably, Marsh Creek’s natural course was altered to better serve the businesses and residents that inhabited the region.

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Glenn Falls

Courtney Bay

Figure 1. Map showing the Marsh Creek watercourse within Saint John, New Brunswick.

Stream Characteristics Marsh Creek is relatively shallow with an average depth of less than 30 cm and width of approximately 6 meters. The creek banks and bottom sediments consist of a very soft, silty layer that is quite thick (>1m in some sections) (Leger and Drake 1998). Much of the banks are covered in thick vegetation and thus much of the creek has been isolated (to a small extent) from public access (Figure 2). Some stretches of the riparian zone have been stripped bare, with others having been reinforced with wooden or rock walls leaving little room for any sort of riparian zone vegetation (Leger and Drake 1998). The creek offers ideal habitat for a variety of local species, including waterfowl, blue heron, raccoons, groundhogs, and deer, and has great aesthetic appeal at first glance. The creek ecosystem is under daily anthropogenic stresses. Its close proximity to heavily developed regions opens it to large influxes of solid waste and urban runoff containing great amounts of petroleum and chemical products. The lower end of the creek has 10 sewage outfalls, which dump millions of liters of untreated human waste on a daily basis (Leger and Drake 1998).

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Figure 2. A picture showing the typical riparian zone of the lower Marsh Creek watershed. The picture was taken at a location approximately 100 metres below the Canada Post property (right side of photo). A creosote recovery device is visible in the distance near the left back.

Creosote Contamination In the fall of 1996, two ACAP Saint John volunteers were surveying Marsh Creek when they noticed small oil sheens appearing on the water surface in the area adjacent to the Canada Post building. A paddle was driven into the bottom which, on upon its removal, revealed a large deposit of a petroleum-based product within the sediments of Marsh Creek. Further studies determined that the petroleum-based product was in fact, creosote, a substance used to preserve wood.

An in-depth study on the property adjacent to the stream revealed that a creosote wood treatment facility once graced these stream banks (Leger and Drake 1998). Specifically, in 1910, Joseph A. Likely established a timber yard on what is now the Canada Post property adjacent to Marsh Creek. Between 1927 and 1936, a creosote treatment plant was constructed within the boundaries of the timber yard (Figure 3). Though its construction date is unknown, the facility first appeared in a Fire Insurance Plan dated 1939. Freshly treated wood was often placed on railroad cars and allowed to drip dry on a bridge that extended across the creek or it was stacked in large piles along the creek banks. As the treated wood sat, excess creosote seeped into the ground and eventually into the creek. The plant continued these practices until it’s closure in 1970. The resulting legacy is a very large creosote deposit with the creek sediments (Mullet 1998).

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Figure 3. An historical picture, taken in the early winter of 1917, of the John A. Likely Timber Yard located on the now Canada Post site adjacent to Marsh Creek.

Characteristics of Creosote The term creosote was first coined by the pharmaceutical industry, in the early 1800’s in reference to a phenolic material derived from Beachwood. Wood creosote is a colorless to yellowish greasy liquid with a characteristic smoky odor and sharp, burned taste. It is composed of primarily phenols, cresols, and guaiacol (NSC 2003). This substance was used to treat chronic bronchitis, as a disinfectant, a laxative, and a cough treatment. Today, it is still used in Japan, along with a number of other countries, as an expectorant and cough treatment (NSC 2003). In 1838 chemists developed a method of distillation, which isolated the tar acid fraction of coal tar.

Coal tar quickly became the most widely used form of wood preservation. Today, coal tar creosote is the most common form of creosote found in the workplace and at hazardous waste sites in the United States (NSC 2003).

Coal tar creosote is a thick, oil-like liquid that is typically amber to black in color (NSC 2003).

The coal tar acid was superior in toxicity and penetration rates compared to that of traditional methods. It also contained a lesser volume of the immobile, heavy molecular weight material.

Thus it was a superior wood preservative and was used to treat such products as railroad ties, telephone poles, marine piling, fence posts and the logs used to construct log homes and cabins.

Creosote is also a restricted-use pesticide, and is used as an animal and bird repellant, insecticide, fungicide, animal dip, and pharmaceutical agent for the treatment of psoriasis (NSC 2003). The wood preservation industry adopted the term creosote in reference to the coal tar acid fraction 7

(Embos-Mattingly et al. 2001). Today the term creosote, as defined by the American Wood Preservation Association, refers to: A distillate of coal-tar produced at high temperature carbonization of bitumous coal; it consists principally of liquid and solid aromatic hydrocarbons and contains appreciably quantities of tar acids and tar bases; it is heavier than water, and has a continuous boiling range of approximately 275oC, beginning at about 175oC (Konasewich 1988).

Creosote was found to have a toxic affect on a wide range of wood-destroying species including fungi, insects, and marine borers. Creosote also repels water effectively, improves dimensional stability and mechanical wear as well as resists corrosion, reduces electrical conductivity and increases resistance to corrosive chemicals (Konasewich 1998).

Initially, creosote was a straight run distillate of the coal-tar acid fraction, but over time, various blends of creosote were developed. These consisted of non-marketable tar by-products, enhanced blends (selected petroleum and tar fractions) and bulking agents. These blends were developed to increase permeability and persistence (NSC 2003). To date, approximately 300 separate chemicals comprise the basic makeup of creosote but it could contain as many as 10 000 chemicals within a single blend (Embos-Mattingly 2001). A further break down of the chemical structure of creosote shows that it contains five separate classes of hydrocarbons: 1) 2) 3) 4) 5)

Polycyclic aromatic hydrocarbons (PAHs) – 90% Heterocycles containing oxygen – 5 to 7.5% Heterocycles containing nitrogen – 1 to 3% Heterocycles containing sulphur – 1 to 3% Phenolics – 1 to 3%

In all, PAHs make up some 90% of all hydrocarbons present in a creosote blend.

Creosote is considered to be a hazardous material and as such has many serious health and environmental concerns. Many of the chemicals present within creosote (such as phenols) are carcinogenic. Direct contact to skin or exposure to vapors in small amounts can lead to sun sensitivity but over an extended period of time it can lead to the reddening, blistering, or peeling of the skin and irritation of the respiratory tract. Direct contact to the skin or vapors in large amounts can result in convulsions, mental confusion, kidney and liver problems, unconsciousness and even death (NSC 2003). The PAHs present in creosote can remain within an environment for an extended period of time in 6 separate forms, including; 1) 2) 3) 4) 5) 6)

particulate pollutants; liquid films; adsorbed to sediment particles; adsorbed to organic matter; dissolved in pore water; and as a solid or liquid phase in pores.

All of these forms can be found within the Marsh Creek ecosystem.

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The concentration of the creosote deposit within Marsh Creek has been recorded at levels as high as 700 000 ppm, which roughly translates into a ratio of 70% creosote to 30% sediment. With such a high concentration of creosote, the Marsh Creek deposit could have serious health risks associated with direct contact (Leger and Drake 1998). But, when combined with the large daily influx of raw sewage, the area under review posses as a major health and safety hazard for both inhabiting species and human contact.

Remediation Methods in Marsh Creek In the fall of 1996 a Phase I assessment, performed by Fundy Engineering, confirmed the presence of creosote in the Marsh Creek sediments (based on the presence of PAHs within stream bed sediments). Subsequently, Canada Post (the current owner of the property adjacent to the contamination site) performed a Phase I and II assessment on their property. As part of the Phase II assessment, Canada Post inserted a steel retaining wall along the edge of their property adjacent to Marsh Creek. They also installed collection wells along their property next to the creek to collect any creosote, which may still be seeping from the property (Figure 4). These wells are monitored and, when necessary, pumped out on a regular basis.

Figure 4. A diagram showing the location of sample wells and steel retaining wall placed adjacent to the Canada Post property.

In 2002, ACAP Saint John performed a study on remedial options to remove the creosote from Marsh Creek. Various methods of remediation were reviewed and their overall cost : effectiveness ratios were compared. It was determined that passive transport devices (PTD) would be the best and most cost effective method to remove creosote from the soft sediment of Marsh Creek. Two types of passive transport devices were designed and implemented by ACAP staff (Isaacs 2002).

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The first device developed was called the Horizontal Recovery Device (HRD) (Figure 5). This device was designed specifically to target the creosote in the small sand partition of the brown clay/silt layer of the substrate. The dimensions of the device are 1.3m high x 1.3m long x 10 cm wide. The form was constructed from enhanced steel and both angle and channel iron. Two layers of polyethylene geotextile were placed on each side of the frame. In theory, the geotextile would serve as a filter that allowed only water and creosote to move into the device where it would collect and later be removed. To reinforce the geotextile, a layer of steel mesh was placed on top. This improved the strength and rigidity of the device as a whole.

The second device developed was called the Vertical Recovery Device (VRD) (Figure 5). The VRD is similar to a well point, and was constructed with a piece of 10 cm diameter 20 slot screen PVC pipe. The pipe was cut to 1.6 m in length and a screw-on well point was place on one end and a slip cap on the other (these devices were pre-ordered and came fully assembled). The VRD is driven down into an area of known creosote concentration and the product will seep through the slotted-length (slots are too small for most silt particles) in which it then collects at the bottom. The product is then extracted from the device via a peristaltic pump.

VRD HRD

Figure 5. A picture showing the implemented HRD (left) and VRD (right) creosote remediation devices within the Marsh Creek sediments.

In 2003, a closer look at the operational efficiency of both the HRD and VRD was initiated. The total volume of creosote removed, the ease of implementation and cost of construction was compared between the two PTD to determine which device was most efficient. Overall, the VRD was the least expensive to construct with a total cost of approximately $110 per unit compared to the HRD with a total cost of approximately $400 per unit (Bates et al. 2003). The HRD weighed roughly 90 kg and thus required the use of heavy equipment (backhoe) to be inserted into the stream sediments. The VRD, however, weighs approximately 3 kg and is easily placed within the stream sediment by hand. The VRDs out performed the HRDs consistently in the uptake of 10

creosote from the sediment. Both devices were set approximately 1m from each other to ensure that the difference in creosote volumes was not due to location. Based on these results, the VRDs had a higher operational efficiency and thus were considered the best device for further remediation efforts within Marsh Creek (Bates et al 2003).

Phytoextraction of PAHs by Aquatic Plants in Marsh Creek Plants are somewhat indiscriminant when it comes to which compounds they remove from their surrounding environment. As long as the particles are small enough (contaminants and nutrients alike), plants are be able to uptake them through their roots. Phytoextraction is the process whereby plants absorb contaminants from their local environment and store them within their tissues (Belz 1997).

The ability of plants to phytoextract various contaminants varies greatly between genus and species. Research on this topic is still relatively new, and as such, is unclear as to how much of a specific contaminant (such as phenols or PAHs) a particular species may extract. Thus, it is imperative to determine if the local species within Marsh Creek are up taking these contaminants and if so, the concentrations of the contaminants that are being held within their tissues. The results could provide insights into the potential for creosote-related contaminants to enter the food chain.

Objectives of the 2004 Marsh Creek Remediation Project The objectives of the 2004 Marsh Creek Remediation Project were to; 1. Implement the largest (to-date) extraction of creosote from the sediments of Marsh Creek; 2. Identify the specific human health hazards associated with the creosote contamination; 3. Determine if aquatic vegetation in Marsh Creek was incorporating creosote-related contaminants within their tissues; and, 4. Increase public and governmental awareness of the importance of pursuing strategies to remediate the creosote contamination in Marsh Creek.

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Methods Active Extraction of the Passive Transport Devices At the completion of the 2003 Marsh Creek Remediation project, all of the PTDs (VRDs and HRDs) were left within the creek to collect creosote over the winter. Marsh Creek rarely freezes to any great depth, and often exhibits sections continuous open flow, especially in the lower sections. For added protection, the VRDs were push down into the sediment, only leaving about 15 cm remaining above the creek bottom. Unexpectedly, the creeks water level remained extremely low, exposing the VRDs to open air. As well, the winter of 2003 was exceptionally cold resulting in a greater than usual build-up of ice. As such, two of the four VRDs were damaged during the winter months, one of which was irreparable. The HRDs faired much better. during the winter months. Their steal frame withstood the ice buildup, although one was battered quite severely. It was, however, easily repaired. Of the original eight PTDs placed within Marsh Creek during the 2003 study, only six were still useable in the 2004 study.

On July 23, ten new 10 cm diameter VRDs and three 5 cm diameter VRDs (left over from the initial study in 2002) were placed within the sediments of Marsh Creek (Figure 6). The distribution of the devices was based upon the volumes of creosote removed in 2003, and were concentrated within three sites. Site 1, adjacent to the Canada Post property, received 8 new devices, seven 10 cm and one 5 cm. Site 2 had two 10 cm and two 5 cm devices while site 3 only had one new 10 cm device implanted within the sediment (Figure 7). The implementation of these devices required a Water Course Alteration Permit (ALT 18087’01), which had been acquired previous to July 23.

Figure 6. ACAP staff install creosote vertical recovery devices (VRDs) into Marsh Creek, on July 23, 2004. Sheens of creosote liberated from the sediments are visible in the photo on the right. A concrete support from a railroad bridge that once crossed Marsh Creek is visible in the background of the picture on the right.

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Figure 7. The distribution of creosote recovery devices in Marsh Creek in 2004. Three general areas were targeted (S1/S2, S3, and S4/S5) based upon the results obtained in the 2003 study.

Although creosote contamination has migrated some distance downstream, the heaviest concentrations are located within the 200 metre section between sites S1 and S5.

The devices were then pumped every two weeks via a peristaltic pump (Figure 8) and the amount of creosote removed was measured and recorded. Devices that were not producing significant volumes of creosote were moved to those sites, which had the highest volumes. The creosote was pumped into 20L pales and stored on site in a lock box. When an excess of 80Ls was collected, Clean Harbours (1-800-361-2209, ext. 234), a waste treatment company, retrieved the product for the appropriate treatment (NB Generator # - NB005625). At the completion of the 2004 project, all of the VRDs were removed from the creek while the HRDs were allowed to sit for the winter. Each of the removed devices were cleaned with use of acetone and stored for the winter. All of the used acetone was then collected within a 20 litre pale to be picked up by Clean Harbours for proper treatment.

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Figure 8. ACAP staff demonstrate the peristaltic pump used to extract creosote from the passive recovery devices (left). The success of the devices in collecting creosote on any given date could be visibly determined by the colour and consistency of the fluid emanating from the output tubing of the peristaltic pump (right).

Phytoextraction Test for PAH’s in the tissues of Aquatic Plants in Marsh Creek On September 1, 2004, aquatic plants were collected from two locations in Marsh Creek. Two species were collected in the downstream site in the area of known high creosote concentrations, and one species was collected over a kilometer upstream of the heavy creosote contamination.

The species were the dominant aquatic vegetation in each respective area.

Some samples were sent to the New Brunswick Museum for taxonomic identification, and the remainders frozen until they could be analyzed for the presence or absence of PAH’s. The samples were analyzed at The University of New Brunswick in Saint John. A Soxhlet extraction (Figure 9) was performed and the extract was separated via Thin Layer Chromatography (TLC).

Samples of the plants were also sent to Environment Canada to be identified and analyzed to greater precision. The materials and procedure for the Soxhlet Extraction Procedure is as follows; Apparatus 250ml round bottom flask Allihn Condenser Heating mantle Ring stand with clamps Wire Glass thimbles Zymark Turbo-Vap 500 closed cell concentrator 100ml graduated cylinder

Soxhlet Extraction Tube Hosing Glass wool Mortar and Pestle

Chemicals Hexane Naphthalene Boiling chips

Sodium Sulfate Methylene Chloride

Acetone Anthracene

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Procedure Perform ALL analysis in a fume hood with the shield pulled down. Safety glasses and lab coat must be worn at ALL times.

Apparatus Assembly ! Place flask in the heating mantle and secure to ring stand with clamps. ! Place Soxhlet extraction tube on flask and secure to stand with clamp. ! The Allihn Condenser will fit on top of the extraction tube also secure to stand with clamps. ! Connect water inlet line to the bottom of the condenser. ! Connect water outlet line to the top of the condenser. ! Wire all water connections.

Sample Preparation ! Prepare a 50:50 mixture of Hexane and Acetone (100ml of each hexane and acetone). ! Rinse samples. ! Allow samples to come to room temperature. ! Weigh out sample. ! Grind sample with a mortar and pestle with sodium sulfate. ! Place sample in thimble. ! Put a plug of glass wool in the thimble on top of the sample. ! Place 100ml of hexane and 100ml of acetone in round bottom flask. ! Turn heating mantle to approximately 60. ! Let mixture reflux for 18 hours. ! Observe at least two reflux actions to ensure proper operation. ! Take extract and place in a separatory funnel. ! Add approximately 150ml of DI water. ! Mix water and extract to remove the acetone. ! Drain off water. ! Rinse the hexane three times with DI water and drain the water off each time. ! Drain off hexane. ! Concentrate hexane in the Turbo-Vap concentrator. ! Use Thin Layer Chromatography (TLC) to qualitatively determine if plant tissues are absorbing PAHs. (Cook)

Analysis Using Thin Layer Chromatography (TLC) • If large glass plates are being used, use a glass cutter and cut plates to appropriate size.

• Score on glass side with adsorbent facing down using a straight edge.

• Snap on the edge of a solid surface.

• Place a pencil line approximately 1-1.5cm from the bottom of the plate.

• Place approximately 1mg of standard Anthracene and Naphthalene separately in a watch glass or test tube and dissolve in a small amount of methylene chloride.

• When spotting the plate with standards and sample make spots at least 1cm from the edge

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• • • • • • • • •

of the plate and at least 1cm from other spots Dip separate capillary tubes into each standard and touch the pencil line on the plate to deposit the standards, taking care not to puncture the adsorbent.

Dip another capillary tube into the concentrated sample and touch the pencil line on the plate to deposit the sample, taking care not to puncture the adsorbent.

Find a jar with a tight fitting cover and place approximately 0.5-1cm of Hexane in bottom of jar.

Put cover on jar and let sit to saturate the inside of the jar with solvent vapours.

Place TLC plate inside jar making sure the solvent level does not touch the spots or the pencil line.

Watch the Solvent front creep up the plate, but do not let it reach the top of the plate.

Let the plate dry in a fume hood.

Use an ultra violet lamp to view the spots. Use the short wavelength to view Naphthalene and the long wavelength to view Anthracene and chlorophyll.

When viewing the spots circle them with a pencil just in case they disappear later.

(Pavia)

Water Outlet Allihn Condenser Water Inlet Soxhlet Extractor Tube

Thimble

Round Bottom Flask Source: Soxhlet Extractor Apparatus. Sigma-Aldrich online Catalogue. http://www.sigmaaldrich.com/Area_of_Interest/Equip____Supplies_Home/Glassware_Catalog/Extractors.html

Figure 9. Schematic diagram of the Soxhlet extraction apparatus used to extract PAHs from the tissues of aquatic plants in Marsh Creek.

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Results Active Extraction of Creosote From Passive Transport Devices The volumes of creosote removed from each device were first recorded on August 16, 2004 (Figure 10). The largest volumes per device occurred at site 1. Overall, the 10 cm VRD outperformed both the 5 cm VRD and HRD, although a creosote volume obtained from HRD 1 (site 1) was equal to 2 of the four larger VRD at this location, and greater than any other VRD at the other four sites. The smaller VRD collected creosote volumes that were slightly lower those of the HRD. The greatest total volume of creosote (based on individual PTDs) removed on September 1st was again from devices located at Site 1. At Site 1, VRD 1 contained the largest volume of creosote; almost double that of VRD 4, which had the next largest volume. Overall, only 4 larger (10cm) VRD’s had volumes greater than those obtained via the HRD across all 5 sites. Both 5 cm VRD’s (1 and 2) contained no creosote and as such their position was altered. It was found that both of these devices had fractured at the sediment line. Out of 15 devices, only three of the larger VRD and one HRD contained more than 1L of creosote, with the other 12 devices producing between 0.5L and 1L of creosote.

On September 14 the 3 devices at Site 1 again produced the highest volumes of creosote. As with September 1, only four devices (three large VRDs and one HRD) produced more than 1L of creosote. Four of the larger VRD produced between 0.5L and 1L of creosote, with the remaining seven devices producing less than 0.5L of creosote (Appendix I). The total volume of creosote removed from all devices was approximately 5L lower than that of the previous extraction.

The final extraction that was measured occurred on September 29, and revealed a similar pattern to the previous three dates with Site 1 again producing the largest volumes.

Overall, VRD 1 consistently produced the greatest volumes of creosote. VRD 4 had the second highest values while VRD 10 recorded the lowest volumes, two of which were 0L. A general reduction in the volume of creosote (when compared to the first extraction on August 16) was observed over time; however, this trend did not hold true at all sites. For example, sites 2 and 6 produced more creosote on the seventh consecutive week of extraction than they did when the site was ‘fresh’.

There were three more extractions performed in which the volumes of creosote were not recorded. The first occurred on August 2 with a total yield of approximately 30L. Two were also conducted after September 29, in which approximately 18L and 20L were obtained on October 13 and November 4, respectively. Difficulties with the equipment, coupled with foul weather prevented the precise measurement of creosote volumes. In total, creosote extractions occurred on seven dates with a total yield of 137 L of creosote (Table 1).

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Figure 10. A histogram indicating the volumes of creosote removed from twelve VRDs on four occasions in 2004.

Table 1: Total volumes of creosote removed during each extraction.

Date Aug. 2 Aug. 16 Sept. 1 Sept. 14 Sept. 29 Oct. 13 Nov. 4 Total

Volume (L) 30 23.2 17.8 15 13 18 20 137.0

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Analysis for PAH in the Tissues of Aquatic Plants in Marsh Creek The identification of the aquatic plants collected in Marsh Creek was conducted by Bruce Bagnall and Gart Bishop. Despite difficulties associated with the identification of samples that were not of optimal quality, they were able to provide with some confidence that Elodea canadensis was collected in both the upstream and downstream sites, while a second sample, consisting of Potamogeton foliosus, was also collected at the downstream site (Figure 11).

Elodea canadensis

Potamogeton foliosus

Figure 11. Plant species collected for analysis of PAH components in their tissues. Elodea canadensis was collected at both the upstream and downstream sites, while Potamogeton foliosus was only observed and collected at the downstream site.

Initial lab trials indicated inconclusive results, because methylene chloride (the solvent used in the development of the TLC plate) was too polar, resulting in the standards and sample ascending the plate on the solvent front. Hexane yielded acceptable results in separating the sample and standards. Time allowed for only three samples to be analyzed. Sample 1 from the downstream site did not yield Anthracene or Naphthalene, but likely contained other PAH. Sample 2 from downstream also did not yield Naphthalene or Anthracene, but also likely contained other PAH. Sample 1 from upstream (being used as a control) also did not show any signs of PAH. ACAP recognized the limitations of the TLC techniques in detecting the presence of PAH, and opted to have the extracts further analyzed by the Environment Canada Lab in Moncton. Results confirmed elevated levels of 11 PAH in the downstream Elodea sample, and 7 in the Potamogeton sample. The upstream sample also showed elevated levels of 4 PAH, although these values were substantially lower than those for the downstream samples (Figure 12, Appendix II).

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PAH Fractions in aquatic plant tissue from Marsh Creek 40000

35000

30000

20000

15000

10000

5000

ph

tha len ap e hth y ac len en ap e hth en e flu o r ph en en e an thr an ene thr a flu cene or a nth en e Be nz py o- A ren -a n e thr a ce Be n nz ch e o( rys Be B) flu en nz e o ( oran K) the flu ora ne B e Ind no nthe z ( ne eo A) (1, py 2 Dib ,3ren en C,D e z( A ,H ) p y B e ) a ren e nz o ( nthr a G, H,I cene )p er y le Tone ta l PA H

0

ac

en

na

nanograms/gram wet weight

25000

PAH Fractions

Figure 12. Histogram depicting the occurrence of PAH fractions in the tissues of aquatic plants occurring in Marsh Creek. Values (indicated as ng PAH per gram wet weight of tissue) are shown for Elodea canadensis upstream ‫ٱ‬, as well as Elodea canadensis ‫ ٱ‬and Potamogeton foliosus sampled downstream at the site of heaviest creosote contamination. Data provided in Appendix II.

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Discussion Active Extraction of Creosote From Passive Transport Devices The higher quantities of creosote extracted from Site 1 (Figure 10) reflect the location of these devices in the area of known highest creosote contamination. From the 1930’s till the mid 1970’s, freshly treated timber would often be left to dry on exposed earth (Figure 3), and on rail cars that occasionally sat on the railroad bridge over Marsh Creek, where Site 1 was situated (Appendix III). Although the bridge no longer extends over the creek, the posts, which supported its structure, can still be seen (Figure 6). This intense concentration may have resulted from the deposition of creosote from rail cars directly onto these sediments coupled with the migration of contaminants from the former lumberyard to the more low-lying topography of the stream bottom.

Overall, the 137 litres of creosote removed from Marsh Creek during the 4-month period (August to November) was considerably higher than in 2003, which yielded some 60 litres of the contaminant (Bates et al. 2003). This increase clearly reflects the greater effort (more devices) directed towards creosote removal, and showed that considerable volumes could be extracted with technologically simple devices. However, the relatively slow decline in volumes collected at some sites, coupled with the fact that one site even showed an increase in collection over time, suggests that the movement and re-distribution of creosote within the sediments may occur at a rate faster than our methods could mitigate. That is, even though the results seem impressive, the extent of contamination is likely great enough to warrant more definitive remediation techniques.

The creosote contamination in Marsh Creek extends well beyond the limits of its banks, and includes a large area beneath the Canada Post property. Although a sheet pile retaining wall has been built to reduce the movement of creosote from this site, it is improbable that this wall could prevent all creosote from migrating off of the site into surrounding areas. As such, the effective remediation of this problem would likely be best accomplished by a combination of the removal of soils and sediments with the highest levels of contamination, coupled with passive recovery devices located in more sensitive areas (i.e. adjacent to buildings, roads, railroad tracks, other permanent infrastructure). These devices will likely have to remain in place for some time until monitoring reveals an acceptable decline in the occurrence of creosote components. Once the most significant concentrations of contamination have been removed, the opportunity exists for bacteria to ‘polish’ the remaining contaminants (D.L. Remediation, personal communication).

PAH in the Tissues of Aquatic Plants in Marsh Creek The occurrence of PAH in the tissues of aquatic plants in Marsh Creek increases the potential for contaminants to migrate from the sediments into the food chain. Plants form the base of every terrestrial and aquatic food web. If plants containing contaminants are consumed, these contaminants can be passed on through the subsequent trophic levels and may even bioaccumulate at each level. The net result can produce deleterious levels of contaminants in the toplevel consumers (Sas-Nowosielka et al 2004).

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Both Elodea canadensis and Potamogeton foliosus are important food sources for waterfowl, and are consumed by other aquatic animals such as muskrats and beavers. The lower sections of Marsh Creek (where the highest levels of PAH fractions in plants were recorded) host an abundance of herbivorous waterfowl year-round. These birds, which include black and mallard ducks, also nest and raise their young in this area. It is highly probable that a large proportion of the forage of these waterfowl consists of plant material containing PAH. The waterfowl in lower Marsh Creek are a food source for raptors such as bald eagles, which have been observed successfully hunting and consuming these ducks during the winter months (Vickers, personal communication). If the waterfowl frequenting Marsh Creek contain elevated levels of PAH, then there exists an even greater threat that the concentrations in top-level consumers like eagles may become deleterious.

These waterfowl may also pose a threat to those humans who hunt migratory birds in the outlying watercourses of the greater Saint John area. Although the extent of dispersion of waterfowl frequenting Marsh Creek is unknown, it is reasonable to expect that emigration does occur. If these emigrant waterfowl are shot and subsequently consumed, the PAH fractions may be absorbed by the hunter or his family.

The majority of the PAH found in Marsh Creek flora are suspected of eliciting a variety of deleterious effects on human health (Appendix IV). Of the four predominant PAH fractions found in Marsh Creek flora, fluorene (the most predominant) has shown mutagenic properties in laboratory animals, and is an irritant of the skin, eyes, liver, and respiratory and gastrointestinal systems. Anthracene can also irritate the eyes, throat and lungs, may act as a sensitizer, and may be a tumor promoter. Acenapthene may be harmful if ingested or absorbed through he skin, causing irritations to the eyes, skin and respiratory system. Lastly, naphthalene can be toxic if inhaled or ingested, and can cause nausea, vomiting, diarrhea, jaundice, kidney and liver damage and hemolytic anemia (breakdown of red blood cells) (MSDS 2005).

The overall effects of a combination of the PAH fractions found Marsh Creek aquatic flora could include irritations to the skin and mucous membranes, including the eyes and respiratory system.

Prolonged exposure could induce pigmentation, cornification of skin surface layers, and telangiectasis, along with headache, nausea, loss of appetite, inflammation of the gastrointestinal tract, slow reactions, weakness, mild liver and kidney damage, and pulmonary degradation. In mice and rats, evidence shows increased liver weights, hepatocellular hypertrophy, reproductive effects, as well as harmful effects on the blood, lungs, and glandular tissues. Additional symptoms could include diaphoresis, hematuria, fever, anemia, liver damage, vomiting, convulsions, coma, confusion, excitement, malaise, abdominal pain, irritation to the bladder, profuse sweating, jaundice, hematopoietic, hemoglobinuria, renal shutdown, and dermatitis.

It is worth noting that a number of PAH fractions were found in the tissues of the aquatic plants sampled upstream in the ‘control’ site. The presence of these compounds may have resulted from one of several sources. PAH are components of hydrocarbon based fuels (i.e. gasoline) as well as tar products. The runoff of hydrocarbons from the numerous shopping center parking lots located upstream of the control site may be a contributing factor. The industrial history of the region also increases the likelihood that additional pockets of contamination do exist along other stretches of Marsh Creek. Public interest in Marsh Creek has resulted in anecdotal stories of 22

former roofing and construction companies dumping tar and oil based products into the watercourse (Vickers, personal communication). Lastly, the movement of the light fractions of the creosote contamination (mainly the PAH) within the watercourse was investigated by ACAP Saint John in 2002 and 2003. The occurrence of PAH in the water downstream of the Canada Post property was routinely documented, and indicated that PAH were likely migrating into the Bay of Fundy from Marsh Creek (Bates et al., 2003). However, sporadic occurrences of PAH were also found is some of the upstream sites. It was suggested that the backflow of the creek during high tidal events could distribute PAH laden waters above the zone of heaviest contamination; however, the actual source of these PAH was never determined (Bates et al., 2003).

Regardless of the source of PAH occurring in the aquatic flora of the upstream control site, the fact remains that aquatic plants inhabiting in the region of highest creosote contamination in Marsh Creek display elevated levels of PAH. It is reasonable to argue that removing the soil and sediment with the heaviest creosote contamination from the creek and surrounding area will alleviate the majority of the risk and environmental degradation associated with PAH in this watercourse.

In summary, the potential effects of human exposure to PAH originating from the creosote contamination in Marsh Creek are serious enough to warrant immediate action. The occurrence, distribution and concentration gradients of the creosote contamination in the lowest reaches of Marsh Creek are well documented, and well understood. No further study on this issue is required as a prelude to remediation. People can access the creek at several locations, and although some warning signage has been posted (Figure 13), the majority of the access points do not indicate the extent of the danger.

ACAP Saint John, in conjunction with the City of Saint John, the New Brunswick Department of Environment and Local Government, and Environment Canada, have collaborated for almost ten years on the ‘Marsh Creek Project’. Our endeavours have resulted in a concise overview of the extend of the creosote contamination in Marsh Creek, including its history, dispersion, and potential implications to the health of our community.

We have also documented the types of remediation options available (ACAP 2003). We believe it is time for the community to actively work in concert to find the means necessary to remove this stigma from the heart of our City. In the last decade Saint John has begun the process of curbing our legacy of degrading urban green spaces for the sake of industrial expansion. Removing the creosote from Marsh Creek would constitute the single greatest remediation of a hazardous site in Saint John’s history.

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Figure 13. Sign warning of the human health hazard posed by Marsh Creek.

Appendix I. Volumes of creosote collected from individual passive recovery devices in Marsh Creek, in 2004.

August 16

Site 1

September 1

4" VRD 2" VRD 2.75 0.5 2 2.25 2

Site 1

0.75 0.75

0

1.5

Site 3

0.5 0.5

0 0.5

0.1 1.75

0.75

Site 4

0.5 0.5

0.75 15.725

0.75 5

Site 5: Seaton Street Total

0.5 1.125

1

Site 3

1 1

0.75 0.75

Site 4

2.5

September 14

Site 1

4" VRD 2" VRD 2.79 0.93 0.47 2.79 0.47

Site 2

1.86 0.93

0

Site 3

0.16 0.32

0 0.32

Site 4

Site 5: Seaton Street Total

4" VRD 2" VRD 3.8 1.5 1 2 0.75

Site 2

Site 2

Site 5: Seaton Street Total

HRD 2

HRD 1.25

0.75

0.75

1.25 13.8

0.5

0.75 3.5

September 29 HRD 1.86

Site 1

4" VRD 2" VRD 2.51 0.85 0.95 1.22 0.37

HRD 2.32

Site 2

0.58 0.45

0

0.16

Site 3

0.32 0.45

0 0.37

0 0.93

0.08

Site 4

0 1.09

0.33

0.93 12.58

0 2.1

Site 5: Seaton Street Total

0.59 9.38

0 3.24

0.32

24

0.37

0.59

Appendix II. Concentrations of polycyclic aromatic hydrocarbon (PAH) fractions found in the tissues of aquatic plants occurring in Marsh Creek, Saint John, New Brunswick.

Concentrations are given as ng of PAH per g of wet plant tissue.

Elodea canadensis

Elodea canadensis

Potamogeton foliosus

Upstream 5.10 5.686

Downstream 4.93 4.902

Downstream 5.2 3.822

PAH Fraction NAPHTHALENE ACENAPHTHYLENE ACENAPHTHENE FLUORENE PHENANTHRENE ANTHRACENE FLUORANTHENE PYRENE BENZO-A-ANTHRACENE CHRYSENE BENZO(B) FLUORANTHENE BENZO(K) FLUORANTHENE BENZO(A) PYRENE INDE0(1,2,3-C,D) PYRENE DIBENZ(A,H)ANTHRACENE BENZO(G,H,I)PERYLENE

ng/g 614 <15 <15 86 <15 78 99 <15 <15 <15 <15 <15 <15 <15 <15 <15

ng/g 3 067 <15 3 580 20 517 1 237 6 768 161 145 683 259 130 105 <15 <15 <15 <15

ng/g 1 401 <15 1 110 3 592 222 1 176 517 <15 132 <15 <15 <15 <15 <15 <15 <15

TOTAL PAH (ng/g)

877

36 652

8 150

Sample Volume Extract (mL) Wet Weight (g)

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Appendix III: Map showing the position of the ACAP Saint Johnâ&#x20AC;&#x2122;s creosote extraction sites relative to historical railroad lines. The occurrence location of Site 1 (S1) below the railroad bridge is clearly evident.

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Appendix IV. The potential effects of some polycyclic aromatic hydrocarbons on human health.

References: The Risk Assessment Information System (Last updated Aug 9th/04) http://risk.lsd.ornl.gov/index.shtml Chemical Backgrounders (Last updated Jan 8th/04) http://www.nsc.org/library/chemical

PAH Phenanthrene

Fluoranthene

Pyrene

Benz(a)anthracene

Chrysene

Benzo(b)fluoranthene

Benzo(K)fluoranthene

Effect on Human Health could be absorbed readily from the gastrointestinal tract and lungs; injections produced slight hepatotoxicity in rats (Yoshikawa et al., 1985)

can be absorbed through the skin following dermal exposure(Storer et al., 1984), and expected to be absorbed from the gastrointestinal tract and lungs.(U.S. EPA, 1988); doses of greater than or equal to 250 mg/kg produced nephropathy, increased liver weights, and increased liver enzyme levels in rats (U.S. EPA, 1988);caused an increased rate of embryo resorptions in pregnant rats(Irvin and Martin, 1987); active as a co carcinogen when applied with benzo[a]pyrene to mice by skin application (Van Duuren and Goldschmidt, 1976) oral exposure produced nephropathy, decreased kidney weights, increased liver weights, and slight hematological changes in mice(TRL, 1989) , and produced fatty livers in rats (White and White, 1939); swelling and congestion of the liver and increased serum aspartate amino transferase (AST) and bilirubin levels in rats (Yoshikawa et al., 1985).

can produce mutations in bacteria and in mammalian cells, and transform mammalian cells in culture; is a component of mixtures that have been associated with human cancer; has produced tumors in mice when exposed Animal studies have shown that approximately 75% of the administered chrysene may be absorbed by oral, dermal, or inhalation (Grimmer et al., 1988; Modica et al., 1983; Chang, 1943); distributed to highly lipophilic regions of the body, most notably adipose and mammary tissue (Bartosek et al., 1984; Modica et al., 1983) ; probable human carcinogen, based on the induction of liver tumors and skin papillomas and carcinomas following treatment and the utagenicity and chromosomal abnormalities induced in in vitro tests has not been tested in any other species other than mice; has produced skin tumours in mice following repeated skin paintings; also an indicator of skin carcinogenesis in mice and produce local sarcomas known to degrade slowly in soil; When it is released into water it will rapidly sorb to sediment;Hepatic and lung tumors occurred in newborn mice receiving 2.1 umol benzo[k]fluoranthene via i.p. injection (LaVoie et al., 1987).

Similar effects of exposed mice could occur in people, but we have no

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Benzo(a)pyrene

Dibenz(a,h)anthracene

Benzo(g,h,i)perylene

Indeno(1,2,3-cd)pyrene Fluorene Anthracene Acenapthene

Naphthalene

information to show that these effects do occur; is rapidly distributed to several tissues in rats (Sun et al., 1982; Weyand and Bevan, 1986);Sub chronic dietary administration of 120 mg/kg benzo[a]pyrene for up to 180 days resulted in decreased survival due to hematopoietic effects (bone narrow depression) in a "nonresponsive" strain of mice Immunosuppression has been reported in mice administered daily intraperitoneal injections of 40 or 160 mg/kg of benzo[a]pyrene for 2 weeks, with more pronounced effects apparent in "nonresponsive" mice (Blanton et al., 1986; White et al., 1985); Mice fed high levels of benzo[a]pyrene during pregnancy had difficulty reproducing and so did their offspring. The offspring of pregnant mice fed benzo[a]pyrene also showed other harmful effects, such as birth defects and decreased body weight; suspected human carcinogen if absorbed through the gastrointestinal tract, it is distributed to various tissues, mostly in the liver and kidneys; No human studies were available to evaluate the toxicity of dibenz[a,h]anthracene. In animals, depressed immune responses were observed in mice following single or multiple injections(White et al., 1985); Weekly injections of 0.05% of the compound for 40 weeks produced lymphoid tissue changes, decreased spleen weights, and liver and kidney lesions in mice(Hoch-Ligeti, 1941); Weekly intramuscular injections of 20 mg/kg promoted the development of arteriosclerotic plaques in chickens (Penn and Snyder,1988) No human or animal data are available to evaluate the toxicity when benzo[g,h,i]perylene was administered simultaneously with benzo[a]pyrene to the skin of mice, an increased incidence of skin tumors was observed compared to the tumor incidence in mice treated with benzo[a]pyrene alone, indicating possible cocarcinogenic activity of benzo[g,h,i]perylene (Van Duuren et al., 1973) a probable human carcinogen (the most predominant in Marsh Creek) has shown mutagenic properties in laboratory animals, and is an irritant of the skin, eyes, liver, and respiratory and gastrointestinal systems Anthracene can also irritate the eyes, throat and lungs, may act as a sensitizer, and may be a tumor promoter.

Acenapthene may be harmful if ingested or absorbed through the skin, causing irritations to the eyes, skin and respiratory system. naphthalene can be toxic if inhaled or ingested, and can cause nausea, vomiting, diarrhea, jaundice, kidney and liver damage and hemolytic anemia (breakdown of red blood cells) (MSDS 2005).

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References 1. Art Cook. Environmental Services, Environment Canada, Moncton.

2. Bates, C., Matthews, T., and Vickers, T. 2003. 2003 Marsh Creek Passive Recovery Project. ACAP Saint John.

3. Belz, Kelly Z. Phytoremediation. 1997. Civil Engineering Department, Virginia Tech.

October 19,2004.

4. Colorado University (CU), Boulder. 2003. CU Boulder Organic Undergraduate Courses.

Lab Techniques. http://orgchem.colorado.edu/hndbksupport/TLC/TLC.html 5. Embos-Mattingly, S.D., Uhler, A.D., Stout, S.A., and McCarthy, K.J. 2001. Identifying creosote contaminated sites: An Environmental Overview. AEHS â&#x20AC;&#x201C; Soil, Sediments and Water.

6. Isaacs, J. 2002. An Evaluation of Remediation Options for Marsh Creek. ACAP Saint John.

7. Konasewich, D.E. 1998. Creosote Wood Preservation Facilities: Recommendations for design and Operation. (Report EPS 2/WP/1). Environment Canada.

8. Leger, B. and Drake, A. 1998. Study of the extent of contamination in Marsh Creek.

ACAP Saint John.

9. Matthews, T. and Vickers, T. 2004. The 2004 Water Quality Monitoring Report for the Greater Saint John Region. ACAP Saint John.

10. National Safety Council (NSC). 2003. Creosote Chemical Background.

11. Pavia, Kriz, Lampman, Engel. Introduction to Organic Laboratory Techniques a Small Scale Approach. Harcourt Brace and Company, 1998.

12. Safety (MSDS) Data. The Physical and Theoretical Chemistry Laboratory. Oxford University. Updated April 7th, 2005 13. Sas-Nowosielska, A., Kucharsk, R., Malkowski, E., Progrzeba, M., Kuperberg, J.M., and Krynski, K. 2004. Phytoextraction crop disposal â&#x20AC;&#x201C; an unsolved problem. Environmental Pollution, Volume 128, Issue 3.

14. Wright, E.C. 1996. The Saint John River and Its Tributaries.

15. Soxhlet Extractor Apparatus. Sigma-Aldrich online catalogue.

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