Characterization of Contaminant and Biomass-Derived Organic Matter in Sediments from the Lower Passaic River, New Jersey, USA

Transcription

1 Characterization of Contaminant and Biomass-Derived Organic Matter in Sediments from the Lower Passaic River, New Jersey, USA Nicole M. Bujalski Michael A. Kruge Earth and Environmental Studies Department, Montclair State University, Ney Jersey, USA

2 Project Goals Understand the processes involved in legacy and ongoing contaminant patterns in the lower Passaic River using an environmental forensics approach Distinctive molecular fingerprints Relation to sediment and contaminant transport

3 We previously reported at PRS: Importance and characteristics of sedimentary biomass land plant, algal, bacterial, sewage PAH and petroleum contamination orders of magnitude greater than dioxin Possible subsurface migration of coal tar (MGP?) into deep PR sediments

4 Methods High resolution sub-sampling of four long (4-7 m) sediment cores from the Lower Passaic River Sediment grain size distribution Molecular organic geochemistry (Pyrolysis-GC/MS) Polycyclic aromatic compounds Petroleum biomarker compounds Biomass pyrolysis products Principal components analysis Integration of results with existing LPRRP data set Chemostratigraphy

5 Sediment Core Locations NY/NJ Harbor Passaic River 7A 9A 10A 5A Hackensack River Upper New York Bay Brooklyn Staten Island Base map: Google

6 Sediment Core Locations Detail Core 10A Core 9A Diamond Alkali Chemical Plant Former Manufactured Gas Plant Core 7A Core 5A

7 Lower Passaic River Water Depth Profile 0 5A 7A 9A 10A Core locations 2 Actual Depth (2004) 65 years deposition 4 6 Water Depth (m) 21 years deposition 8 Authorized Channel Depths 10 River km River Mile Malcolm Pirnie, Inc. 2007

8 Radiometric Age Estimation 137 Cs (pci/g) log 210 Po excess Depth (m) Data: LPRRP, 2008

9 Radiometric Age Estimation Stratigraphic Zonation 137 Cs (pci/g) log 210 Po excess PCBs (mg/kg) 2,3,7,8-TCDD (μg/kg) Depth (m) Data: LPRRP, 2008

10 Radiometric Age Estimation Stratigraphic Zonation 137 Cs (pci/g) log 210 Po excess PCBs (mg/kg) 2,3,7,8-TCDD (μg/kg) Depth (m) Data: LPRRP, 2008

11 Age Estimation & Zonation: Core 5A Data: LPRRP, 2008

12 Age Estimation & Zonation: Core 10A Data: LPRRP, 2008

13 Mean Sediment Grain Size (log 2, μm) Sediment Depth (m) Silty Sandy (Fraction < 2 mm, Mastersizer 2000)

14 Total Organic Carbon (%) 5A 7A 9A 10A Increase Upstream Data: LPRRP, 2008

15 Molecular Organic Analysis Pyrolysis-Gas Chromatography - Mass Spectrometry (Py-GC/MS) Pyrolysis 610 C Sediment Prep Dry at 40 C Advantages: - milligram quantities of dry sediment - minimal sample preparation - no solvents needed - "green chemistry - rapid procedure suitable for sediment screening - robust, reproducible, semi-quantitative Similar to EPA Method 8275a

16 Pyrolysis vs. EPA Method 8270 EPA Method 8270 Data: LPRRP, 2008

17 Molecular Fingerprints mud, light brown Core 7A Sample 01 Upper Sediment Depth (meters) mud, medium brown Sample 25 Mid silt with pebbles, dark sand with pebbles, reddish Sample 37 Lower

18 F0 B2: FCA1 I0 4m+3mF BCN ef F2: Il0 G2: VAN Core 7A, Sample 01 ( m) TIC G3:b ^15 ^16 ^16 DKDF Pr:1 S8 PYR-d10 ^22 FLA ^17 ^18 ^19 ^21 BAN 25 ^23 ^ Upper F0 4m+3mF F2: II0 BT2d DKDF PR PHN+ANT PH Upper: Significant Biomass Input DMP FLA + PYR RET mpyr BAN + CHR phtalate Benzopyrene group ^28 ^30 ^29 ^31 Mid B2: FCA1 2mF BCN N0 ef G2: Il1 15 ^16 Mid: Biodegraded Petroleum Py-GC/MS Raw Data (TIC) 3 Representative Samples Core 7A FCA1 F0 4m+3mF N0 F2: II0 2+1mN S0 ACY DMN ACE DBF FLU mflu PHN ANT MP + MA FLA S8 PYR Methylpyrene isomers pthalate BAN/CHR pthalate Bb/j/kFLA BaPYR + PER Lower Near Sand Lens: Combustion Signature

19 Origin of PAHs in Core Sediments Mid Lower Upper Graphic after Yunker et al., 2002

20 Pyrene (mg/kg) Upper Mid 5A 7A 10A Lower 9A Marker for PAH Contamination in Core Sediments

21 Markers for Petroleum Contamination C29 + C30 Hopanes Estimated (mg/kg) Upper Mid 5A 7A 10A Lower (Red ovals: elevated PAH contamination) 9A

22 What about the biomass present in the river sediments?

23 Vinyl Guaiacol and Indole (VGI) Ratio m/z: 124, 138, 150, 164, 152, 166 RT: NL: 4.61E5 m/z= VG Guaiacol Propenyl F: MS PR7AS010259_P Methyl Guaiacol Vinyl Guaiacol Vanillin Time (min) Lignin (Land Plant Derivation) Acetovanillin RT: NL: 1.22E6 90 m/z= I VGI = F: 70 [I + VG] MS Indole PR9AS _P VG Protein (Aquatic Biomass) Methyl Indole m/z: Time (min) Pyrolysis GC/MS Core 7A: Sample 1 (0-7.5 cm)

24 VGI Ratio (Higher: more land plant biomass; Lower: More aquatic biomass) 5A 7A 10A 9A Highest Aquatic Mouth Terrestrial Input Increases Upstream

25 "Combustion" Phenanthrene + Pyrene Summary of Molecular Results (Pyrolysis) Upper Mid Lower All 4 Cores "Petroleum" C29 + C30 Hopanes "Biomass" Indole + Vinylguaiacol

26 Conclusions Recognition of 3 chemostratigraphic zones in all 4 cores PAH contamination ranges from "serious" to "extreme" Notable in lower zone "pyrogenic signature" Associated with sandy lens in Core 7 (near former MGP) Petroleum contamination distinctive Notable in middle zone Biomass relatively more abundant in upper zone Aquatic signature closer to river mouth tidal influence Land plant signature upstream fluvial influence

27 Consider - PR sediments are very organic-rich: Hydrocarbon contamination & biomass Approaching fuel-grade Something like Canada's Athabasca tar sands Alternate solution to disposal of dredged materials: Advanced fluidized bed reactor Energy generation (electricity, steam) Clean residual sediment for beneficial reuse Eliminates vexing disposal issues

28 Our thanks to: Malcolm Pirnie, Inc. (J. Atmadja & E. Garvey) Passaic River Institute (K. Barrett) K. Olsen S. Passchier E. Stern H. Feng J. Galster Dept. of Earth & Environmental Studies (MSU)

29