Organic Pollutants and Heavy Metal Concentrations in Tidal Creek

Organic pollutants and heavy metal concentrations in tidal creek sediments after Hurricane Sandy: A Baseline for susceptible low lying areas in the Hackensack River estuary

Francisco Artigas, Ji Meng Loh, Jin Young Shin, Joe Grzyb and Ying Yao

Abstract

The relatively low cost of lands along with a privileged location near an urban center attracted industry to the Meadowlands estuary and the absence of regulations resulted in vast amounts of industrial waste emitted into the air and dumped to nearby estuaries and marshlands. Hurricane Sandy created an unprecedented sea surge that overtopped berms and tide gates and extensively flooded approximately 2, 280 Ha of a low lying basin that includes Berry’s Creek, a tributary to the Hackensack River and well known for its legacy of contamination The sea surge connected Berry’s with eastern creek that flow into the Hackensack River for several tidal cycles. The objectives were to establish a baseline for organic pollutants and heavy metals post Super Storm Sandy and determine if contaminants from highly contaminated areas moved to the eastern creeks during the surge and finally, measure contaminant gradients around tide gates, Results show that most enriched sediments contained cadmium, mercury and chromium. Concentrations of PCB’s were higher in the western creeks and overall no differences were observed from either side of tide gates. Massive export of contaminants from western to eastern creeks from the sea surge was not apparent. Heavy metal concentrations were greater close to tide gates and may play a role in their distribution across the estuary.

Keywords: Metals, Polychlorinated biphenyls (PCBs), Organochlorine pesticides (OCPs), Tidal creek sediments, Hurricane Sandy

Introduction

Coastal marsh environments provide a unique physical chemical environment with the capacity to immobilize and retain contaminants. Historically, low lying coastal wetlands were viewed as unproductive areas that needed to be transformed into “productive areas” by ditching and filling. The relatively low cost of the land along with a privileged location near urban centers attracted industry which in the absence of regulations resulted in vast amounts of industrial waste emitted into the air and dumped to nearby estuaries and marshlands. The combination of a tidal system with high sulfur and organic matter content along with low redox potentials (Eh) and moderate pH’s provides the conditions for organic pollutants to degrade and metals to be adsorbed to clay surfaces and to precipitate as metal sulfides (e.g. Galena PbS; Cinnabar HgS and Pyrite FeS). Coastal wetlands are among the few ecosystems that support such a unique physical chemical

1 environment that effectively provides the conditions for heavy metals to drop out of solution. The principal form of transport of the existing pollutants is as suspended solids and overland flow as persistent organic pollutants (PCBs and OCPs) and metals associated to the solid phase by adsorption to sediments and organic matter (Adriano 1986; Bohn et al. 1985). Heavy metals are indestructible and will remain as precipitates or adsorbed to organic matter as long as the conditions allow. Persistent organic pollutants on the other hand are man made and are a source of carbon to microorganisms and degrade by undergoing biotic and abotic transformations. The amount of organic pollutants adsorbed to the clay fraction and/or organic matter depends on the compounds distribution coefficient (octanol/water) Kow. Compounds with high Kow will mostly be retained by the sediments and be less available to biological processes1. A normally functioning marsh sustains conditions that limits the mobility of contaminants and with time they are buried under new silt deposits.

Hurricane Sandy created an unprecedented sea surge that overtopped berms and tide gates and extensively flooded approximately 2, 280 Ha of a low lying basin that includes Berry’s Creek, a tributary to the Hackensack River and well known for its legacy of contamination (Citations). A continuous monitoring sensor network recorded water quality and water elevation in the western and eastern creeks before, during and after the hurricane. Water elevation around midnight on October 29th reached 2.8 m which translated into about 1 m of water above street level for most of the study area. Water turbidity almost doubled with the surge and increased almost threefold during the next two tide cycles after the initial surge (Figure 2). Similarly, salinity increased from 9 ppm to 13 ppm during the surge (Chun and Artigas, 2013). The flooded connected the highly contaminated Berrys creek system wuth historically less impacted eastern creeks along residential areas that flow directly into the Hackensack river.

The most contaminated sites occur along occur along the western creeks and belong to EPA’s National Priorities List. (Figure 1. A, C, D and B and E, respectively). Western creeks are known to be contaminated with heavy metals, especially with mercury (Galluzzi and Sabounjian, 1980; Dames and Moor, 1990; Weis et al, 2005). Limited remediation has taken place since contamination was discovered in Berrys creeks complex in the early 1970’s (citation). For decades facilities in this area operated as recovery and recycling centers for off-spec fungicides, pesticides and solvent refining and recovery facilities that left soils and nearby creeks and ditches contaminated with heavy metals, volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) (USEPA. 2006).

1 G. Petruzzelli, F. Gorini, B. Pezzarossa, F. Pedron CNR, Institute of the Ecosystem Studies (ISE), Pisa (Italy) [email protected] 2

A sea surge that lasts over several tidal cycles has the potential to redistribute contaminants by resuspending sediments and moving them around in the flood waters. Sea water also brings metal alkali which have the effect of moving pollutants into solution. This area depends heavily on miles of dikes and numerous tide gates to protect industrial and residential areas from high water. Dikes in this case are elevated earthen embankments 5 feet above sea level designed to keep low lying lands from being flooded during high tides. The presence of tide gates influences oxidation potential (Eh) and pH of surface sediments and affects their mobility l(Portnoy, 1999, Ansfield and Benoit, 1997). Tide gates also change water velocity and affect water turbidity and turbulence from fluctuations between stagnation and flushing flows (Giannico and Souder, 2004). This study has three objectives; 1.- To base line post Super Storm Sandy pollutant levels for a system of tidal creeks, 2.- find evidence that contaminants associated with Berry’s Creek were exported to eastern creeks and 3.- Measure if tide gates play a role in modulating the distribution of contaminants.

Study area

This study includes seven well known creeks and ditches that drain the target area (Figure 1): Eastern creeks that branch off the Hackensack River include: Depyster, Losen Slote and Moonachie. Creeks that are part of the Berrys creek complex include: West Riser, East Riser, Peach Island North and Peach Island East. Also included in the study is a segment of the Hackensack River. . These creeks are part of the towns of Carlstadt, Little Ferry, Moonachie, as well as South Hackensack Township in Bergen County, New Jersey (Figure 1). An outcrop along Washington Ave. in Carlstadt provides the highest elevation of the area at 3 to 5 m and divides the western and eastern creek systems. The average street elevation is 1.5 m and the average elevation of tidal creek banks is also 1.5 m. During Sandy, flood water entering from the western and eastern creeks met at the intersection of the towns of Carlstadt, Moonachie and South Hackensack. Residential areas are close to the eastern creeks while mainly industrial areas exist along the western creeks. Aside from the three super fund sites along Berry’s creek, the entire 2,280 Ha study area also includes more than 20 known contaminated sites (NJDEP 2008).

Figure 1 Map of creeks and sediment sampling locations (black dots) along the creeks and in the Hackensack River. Sites A, B, C, D and E are highly contaminated sites.

Figure 2 Barge Marina depth and turbidity measurements during Hurricane Sandy from 10/26/2012 to 11/1/2012.

Materials and Methods Field Sampling A 12-foot Nasco swing sampler was used to take surface sediment samples from the designated creeks. At each creek, a total of six to nine locations were sampled on the land side of the tide gate. In addition, at each creek, 4 samples were taken from the river side of the tide gate and 5 samples were taken directly from the main stem of the Hackensack River (Figure 1). Three sediment samples at each sampling locations were combined into one composite sample and transferred to a labeled plastic bag. Samples were brought back to the lab and stored in a refrigerator at 4 oC. GPS locations with decimeter horizontal accuracy were recorded at each sampling point using a Trimble GeoXH 6000 Series handheld GPS.

Laboratory Analysis PCB congeners and OCPs: An accelerated solvent extractor (ASE 100, Dionex, USA) was used to extract PCBs and OCPs from the sediment samples by using a mixture of hexane and acetone in a 1:1 ratio. After extraction, gel permeation chromatography (GPC, Autoprep 2000, O I Analytical, USA) was used to clean the samples before GC-ECD. The extracts were concentrated to 1mL by rotary evaporation at a temperature 30°C. The extracted samples were fractioned by florisil column (10mm i.d. x 300 mm length) filled with 10 g of florisil (60-100 mesh; J.T Baker, NJ, activated at 550 °C for 4 hours), and then partially deactivated by the addition of deionized H2O (2.5% by wt.). The sample was loaded into the head of the florisil column and covered with a layer of sodium sulfate to a depth of 10mm. The concentrated extracts were transferred to the florisil column and subsequently eluted with 35 mL of hexane for PCB analysis. A second fraction for OCPs analysis was eluted with 50 mL of dichloromethane and hexane in a 1:1 ratio and collected in a separate vial. Each fraction was solvent exchanged into hexane while concentrated to 5 mL via rotary evaporation. Each sample was finally reduced to 1 mL using a gentle stream of dry nitrogen evaporator (N-EVAP 111, OA- SYS). All samples for 109 PCB congeners and 18 OCPs were analyzed on a gas chromatograph equipped with 63 Ni electron capture detectors (GC-ECD, Hewlett Packard 6890, Santa Clara, CA) with DB-5 (60m x 250 µm in inner diameter x 0.25 µm film thickness, J&W Scientific, CA). The temperature program of GC oven condition was as follows: 100 oC held for 2 minutes; 4 oC/min to 170 oC, 2 oC/min to 280 oC, 1 oC/min to 290 oC; total time, 84.5 minutes. Congeners were identified based on relative retention time. Calibration standards were diluted in acetone from a stock mixture of 20 organochlorine pesticides and PCB congeners, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5 and 1 ppm. Daily single point calibration was also used to generate response factors for each congener relative to internal standards. Two internal standards, PCB 30 (2,4,6- trichlorobiphenyl) and PCB 204 (2,2’,3,4,4’,5,6,6’-octachloro biphenyl) (AccuStandards, CT) were added before analysis, which are not present in commercial Aroclor mixtures. The following surrogate standards (AccuStandards, CT): PCB 14 (3,5-diichlorobiphenyl), PCB 65 (2,3,5,6-tetrachloro biphenyl), PCB 166 5

(2,3,4,4,5,6-hexachloro biphenyl), and Dibutylchlorendate were used in this study as well. These surrogates were spiked to the sample prior to extraction and recovery rate were calculated after analysis.

Metal: Metal concentrations were determined using EPA Method 3051A for microwave-assisted acid digestion of sediment (US EPA Method 3051A). In a microwave digestion vessel, 0.2 g of sediment sample was digested with 7 mL of ultrapure nitric acid (HNO3, 67-70%, w/w, EMD). Standard reference material 1944 (New York/New Jersey Waterway Sediment, NIST) was digested with samples for quality control. After digestion, the samples were diluted to 15 mL with ultrapure water and stored in polypropylene centrifuge tubes at 4°C for further analysis. Solutions were analyzed using an Atomic Absorption Spectrometer (AAS, Varian SpectrAA 220FS). Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn were analyzed using the flame and Hg was analyzed using the cold vapor method.

Geoaccumulation Index (Igeo) The Geoaccumulation Index (Igeo) (Muller 1979) is used to gauge the degree of anthropogenic influence on heavy metals concentration from sediment samples by taking into account the background levels of heavy metals in the principal soil types of the area which in this case belong to the Udorthent and Dunellen soil series (NJDEP 1997). The Igeo is calculated using the following equation:

!! �!"# = ��! (1) !.!!!

Where CM is the metal concentration in sediment sample, BM is the metal concentration in the principal soil types of the area and the background matrix correction factor is 1.5. The Igeo classes (Table 1) are indicating the level of contamination.

Table 1 Sediment contamination classes according to Igeo (Muller 1979; Singh et al. 1997)

Igeo class Value Classification 0 ≤ 0 Practically uncontaminated 1 0-1 Uncontaminated to moderately contaminated 2 1-2 Moderately contaminated 3 2-3 Moderately to heavily contaminated 4 3-4 Heavily contaminated 5 4-5 Heavily to extremely contaminated 6 >5 Extremely contaminated

Statistical Methods The Bartlett test was used to test for homogeneity of variances between the land-side, river-side and river- stem data values while the nonparametric Kruskal test and Analysis of Variance (ANOVA) without assuming equal variances were used to test for differences in their mean values. Estimates of pairwise differences in 6 means were obtained using the Tukey HSD method which provides p values adjusted for multiple comparisons. The non-parametric Wilcoxon test was used to test for differences in means between land-side and river-side measurements for each creek. The standard correlation test was used to test for significant correlations between pairs of metal and organics measurements. Log-linear models were used to investigate any relationships between land-side measurements with distance from the tide gate.

Results Geoaccomulation index

When natural background levels of heavy metals from area uncontaminated soils are taken into account, surficial sediments from eastern and western creeks and the main stem of the Hackensack River are enriched with Cd to a point where they are considered moderately contaminated (Table 2). Sediments from the eastern creeks draining mainly residential areas show low to moderate enrichment for all metals. Western creeks draining mainly industrial areas on the other hand, show moderate to heavy enrichment with Cd, Cr and Hg.

Table 2 Geoaccomulation Index for selected metals from seven creeks and the Hackensack River

Igeo Cd Cr Fe Hg Mn Ni Pb Zn Hackensack River 1.16 1.02 0.31 1.19 0.17 0.54 0.11 0.52 Depyster 1.07 0.57 0.59 0.80 -0.11 0.44 0.25 0.65 East Riser 1.12 0.68 0.18 1.51 0.22 0.40 0.09 0.62 Losen Slote 1.05 0.03 0.08 0.14 -0.24 0.36 -0.06 0.38 Moonachie 1.06 0.61 0.36 0.77 -0.18 0.45 0.01 0.55 West Riser 1.32 0.92 0.14 1.87 0.38 0.47 0.22 0.71 Peach Island North 1.23 0.82 0.13 1.64 0.28 0.50 0.05 0.76 Peach Island East 1.85 1.45 0.36 2.40 0.02 1.04 0.24 1.05

Metal distribution

Berry’s creek Peach Island North and Peach Island East in proximity to site D are the most impaired creeks with the average pollutant concentration more than doubled that of all other creeks. Peach Island East showed the highest concentrations for all pollutants. Further inspection of pollutant concentration in creek sediments shows that Cr, Hg, PCBs and OCPs have the greatest dispersion of values around the mean. Pb and to a lesser extent Zn were found at comparable concentrations in all creeks and with the least dispersion around the mean (Table 3).

Table 3 Average concentration of metal (mg/kg) and organic pollutants (* µg/kg) in all creeks sampled along with the NJ Non-residential Soil Clean up Criteria, the ERL criteria for marine sediments (Long 1995)and Canada Probable Effects Limit (PEL)

Location Cd Cr Cu Hg Mn Ni Pb Zn PCB* OCP* Hackensack River (N=5) Mean 6.61 207.52 136.17 4.29 548.09 50.94 160.72 328.59 73.31 12.60 SD 0.24 39.81 38.18 0.45 92.72 4.27 14.31 41.91 41.51 3.33 Depyster (N=12) Mean 5.37 72.66 131.84 1.76 289.44 40.53 226.56 440.42 138.30 34.80 SD 2.55 76.93 64.42 1.55 174.14 9.51 87.51 117.84 94.78 17.96 East Riser (N=12) Mean 6.06 93.96 113.38 8.95 613.67 36.61 156.62 414.66 218.19 48.61 SD 2.63 87.50 49.06 9.84 477.38 10.46 46.84 223.64 297.45 91.12 Losen Slote (N=13) Mean 5.09 21.05 82.06 0.38 215.23 33.82 109.69 237.92 70.59 36.21 SD 1.27 15.84 63.82 0.35 162.90 13.21 75.90 199.40 59.16 45.66 Moonachie C. (N=12) Mean 5.25 81.21 132.98 1.63 247.44 41.21 129.14 349.08 101.37 19.24 SD 0.99 46.33 94.85 1.59 85.04 13.58 51.39 252.50 105.26 18.81 West Riser (N=10) Mean 9.49 164.96 165.82 20.62 900.56 43.08 209.98 506.33 379.11 143.94 SD 4.16 94.60 99.99 16.02 1098.61 13.98 148.03 235.21 534.93 267.24 Peach North (N=10) Mean 11.00 276.28 179.90 23.35 1349.93 59.78 164.47 588.26 519.88 96.25 SD 11.66 479.33 85.07 38.12 1361.27 20.84 55.62 349.53 551.98 105.87 Peach East (N=10) Mean 24.59 426.90 433.94 51.78 1114.45 136.20 207.73 885.08 1207.92 267.18 SD 24.41 373.25 348.34 48.08 1378.35 118.49 60.87 572.84 939.44 468.67 All Creeks (N=84) Mean 8.97 154.68 168.54 13.45 547.36 52.56 169.36 466.91 307.22 76.83 SD 11.14 246.32 170.34 27.16 722.08 51.91 86.71 338.94 537.99 202.06

NJ Soil Clean- 100 240 600 270 N/A 2400 600 1500 2000 N/A up Criteriaa Effects Range 1.2 81 34 0.15 N/A 21 47 150 23 N/A Low (ERL)b Canada PEL 4.2 160 108 0.7 N/A N/A 11.2 271 189 N/A a Non Residential b Marine Sediments

Organic Pollutants

Peach Island East showed significantly larger PCBs and OCP concentrations compared to all other creeks although only PCB differences were significant at (p<0.05). Creeks included in the Berry’s creek complex exceeded the ERM criteria by at least two fold while none of the eastern creeks exceeded the ERM for total PCB’s (Table 4). Similarly, concentrations of α, β, δ and γ-hexachlorocyclohexanes (BHC) were highest in the Berrys creek complex (Peach Island East, Peach Island North and West Riser, respectively). Out of the eighteen OCPs analyzed, Endosulfan Sulfate showed the highest average concentration 19.79 (µg/kg) followed by dichlorodiphenyldichloroethane (DDD) 9.98 (µg/kg) and Endrin 7.69 (µg/kg). Among these three pollutants only DDD has established ERM criteria (48 mg/Kg) which is not exceeded. The lowest concentrations were Heptachlore Epoxide 0.54 (µg/kg), β-BHC 0.07 (µg/kg) and Endrine Aldehyde 0.01 (µg/kg) (Table 4). The natural degradation products of DDT (i.e. DDE and DDD) were higher and more commonplace than DDT.

Table 4 Average concentration plus Standard Deviation of ∑ PCBs (109), total organochloride pesticides (OCPs) and individual OCP’s (18) for each tidal creek and river channel (µg/kg) and the probable effect level (PEL) from Canadian Sediment Quality Guidelines (Canadian Council of Ministers of the Environment (CCME) 1995)

PCB OCP α-BHC β-BHC δ-BHC γ-BHC Heptachlor Aldrin HP E1 Dieldrin DDE Endrin EII DDD EA ES DDT EK MXC Hackensack River Mean 73.31 12.60 0.37 0.00 5.60 0.00 0.45 0.03 0.18 0.13 0.25 1.44 2.20 0.00 1.76 0.00 0.00 0.00 0.19 0.00 SD 37.13 2.98 0.24 0.00 2.49 0.00 0.17 0.06 0.09 0.12 0.06 0.81 1.20 0.00 0.70 0.00 0.00 0.00 0.38 0.00 Depyster

Mean 138.30 34.80 0.56 0.18 7.42 0.17 2.01 0.67 0.77 0.46 0.99 4.12 3.76 0.61 9.25 0.00 0.77 0.09 2.97 0.00 SD 94.78 17.96 0.43 0.35 8.95 0.42 3.51 2.13 0.47 0.43 0.69 2.64 3.71 1.49 8.78 0.00 1.68 0.31 6.10 0.00 East Riser Mean 218.19 48.61 0.28 0.03 18.30 0.08 2.10 0.07 1.25 1.09 2.52 4.00 12.43 0.18 4.69 0.00 0.27 0.00 0.93 0.38 SD 297.45 91.12 0.44 0.12 52.85 0.28 5.64 0.10 2.78 2.39 3.78 4.46 23.57 0.33 7.74 0.00 0.94 0.00 1.69 1.33 Losen Slote Mean 70.59 36.21 0.17 0.12 2.26 0.13 0.59 0.12 0.42 0.11 0.43 2.94 0.90 0.26 21.79 0.00 1.16 0.03 3.41 1.37 SD 59.16 45.66 0.27 0.24 1.60 0.32 0.87 0.24 0.55 0.19 0.55 4.50 1.72 0.50 33.51 0.00 2.25 0.10 7.34 1.88 Moonachie Mean 101.37 19.24 0.09 0.04 2.55 0.07 0.46 0.01 0.21 0.57 0.70 3.13 4.69 0.14 4.18 0.00 0.33 0.00 1.62 0.44 SD 105.26 18.81 0.20 0.14 2.00 0.26 0.73 0.04 0.28 1.08 0.71 3.17 6.67 0.33 5.18 0.00 1.13 0.00 3.66 1.09 West Riser Mean 379.11 143.94 2.55 0.00 79.59 0.00 5.10 0.01 0.24 2.00 6.76 4.87 5.70 0.08 10.77 0.00 20.79 0.00 3.51 1.96 SD 534.93 267.24 6.59 0.00 216.78 0.00 12.30 0.03 0.26 6.14 14.40 7.07 8.67 0.15 14.05 0.00 49.89 0.00 6.82 5.23 Peach North Mean 519.87 96.24 0.31 0.06 4.37 0.94 9.76 6.70 0.56 1.77 0.46 9.87 3.01 16.42 12.03 0.05 5.87 3.45 14.12 6.49 SD 551.98 105.87 0.25 0.20 8.89 1.46 13.38 10.39 0.54 1.93 0.36 12.11 2.89 25.42 16.89 0.17 8.23 5.99 21.74 11.99 Peach East Mean 1125.27 244.79 1.50 0.06 18.02 0.49 9.41 3.72 0.33 1.09 2.44 11.32 24.08 15.17 11.32 0.05 118.54 2.85 13.04 11.37 SD 932.43 450.77 2.25 0.19 47.01 0.95 12.33 6.33 0.47 1.72 3.50 11.13 25.56 23.99 15.75 0.16 363.34 5.86 10.03 11.60 All Creeks Mean 345.27 83.13 0.72 0.07 17.03 0.25 3.87 1.47 0.54 0.94 1.89 5.47 7.69 4.29 9.98 0.01 19.79 0.83 5.36 2.93 SD 555.43 204.86 2.50 0.21 80.99 0.71 8.72 4.82 1.16 2.53 5.58 7.47 15.17 13.85 17.45 0.08 135.59 3.20 10.56 7.23 PEL* 189 0.99 2.7 4.3 374 62.4 7.81 4.7

* PEL: Probable Effect Level, dry weight HP: Heptachlore Epoxide E1: Endosulfan I E2: Endosulfan II ES: Endosulfan Sulfate EA: Endrin Aldehyde EK: Endrin Ketone MXC: Metoxychlor

Correlations among metals and organic compounds

A test for correlations at p<0.01 among the various metals and persistent organic pollutants (POP’s) in tidal creeks are shown in Table 5. All significant correlations are positive. Hg and Cr where the most highly correlated metals (R-squared = 0.95), followed by Hg-Cd, Ni-Cd, Zn-Cd and Zn-Cu. Cadmium was highly correlated with Hg, Ni and Zn. The two persistent organic pollutants (PCBs and OCPs) were also highly correlated (R-squared = 0.84), yet they were not well correlated to other metals. The high levels of PCBs and OCP associated with the Berry’s creek complex shows a strong relationship to nearby point sources from highly contaminated sites formerly involved in organic waste processing and manufacturing of specialty organic chemicals containing PCBs, OCPs and VOCs.

Table 5 Correlation between metals and organics. Significant correlations at the 0.01 level after a Bonferroni correction are highlighted in bold.

Principal Component Analysis (PCA) loadings on the metals and organic pollutants are shown in Table 6. The top three PCA’s accounted for approximately, 50%, 15% and 12% of the variance, respectively. PCA shows that Cd, Cr, Cu, Hg, Ni, and Zn cluster around the higher end of the PC1 axis and together make up the core of metal pollutants in the creek system. Pb and Zn on the other hand cluster along the PC2 axis which may suggest a common non-point type emission source. Finally, PCB’s and OCP’s cluster around negative values of the PC2 axis suggesting similar sources.

Table 6 Principal Component Analysis (PCA) on the metal and organic pollutants concentration.

PC1 PC2 PC3 Cd 0.393 0.175 -0.196 Cr 0.361 0.021 -0.160 Cu 0.379 0.057 -0.029 Fe 0.082 0.276 0.671 Hg 0.397 0.007 -0.177 Mn 0.064 -0.281 0.128 Ni 0.358 0.018 -0.137 Pb 0.198 0.239 0.575 Zn 0.387 0.214 0.015 PCBs 0.239 -0.580 0.171 OCPs 0.170 -0.608 0.242

Distribution of pollutants around tide gates

A tide gate represents a physical barrier between the river-side and the land-side of a tidal creek. Tide gates are usually located at the mouth of creeks and coincide with the lowest elevations of a creek. Sedimentation rates increase sharply around tide gates as suspended solids and associated contaminants drop out of the water column during stagnation periods. When the log-transformed metal concentrations from all creeks were compared between land-side, river-side and river channel using ANOVA (unequal variances) (Figure 3), we find that Cr is significantly higher in river-side and river channel locations (p value < 0.01). The nonparametric Kruskal test yielded similar findings. Mercury was also higher on the riverside locations but differences were not significant. Zink on the other hand showed significantly higher concentrations on the landside locations and so did Pb, but the difference in this case was not significant.

Figure 3 Boxplot of metal concentration (mg/kg) by land-side, river-side and river channel.

When metal concentrations on the land and river-sides for each tidal creek was tested separately (Figure 4), we find that metals at Depyster Creek (DP), were always higher on the river side with the exception of Zn and Pb. There is no clear pattern in terms of metal concentration for the majority of the creeks with the exception of Peach Isalnd East where metal concentrations were usually higher on the land side. This pattern was contrary to all other creeks were concentrations are similar or higher on the river side with the exception of Cd. (Figure 4).

Figure 4 Logarithm boxplot of metal contaminant concentration (mg/kg) by creek, separating land-side and river-side measurements. (DP: Depyster; ER: East Riser; LS: Losen Slote; MC: Moonachie; PE: Peach Island East; PN: Peach Island North; WR: West Riser; R: Hackensack River.)

As shown in Figure 5, when PCBs and OCPs concentrations were compared between land-side, river-side, and river channel, no significant differences (p<0.05) in the concentrations of total PCBs and OCPs were found (Figure 5).

Figure 5 Boxplot for PCBs and OCPs concentrations (µg/kg) by land-side, river-side and main stem of the river.

Results show that when concentrations of PCBs were compared between land-side and river-side and by tidal creek (Figure 6), overall western creeks (Peach East, Peach North and Moonachie) had higher concentrations of PCB’s on both sides of the tide gates compared to the eastern creeks. When analyzed by creek, Depyster and Peach Island North were higher on the riverside while all others were higher on the land side (Figure 6).

, µg/kg

PCBsconcentrations

Figure 6 PCBs concentrations (µg/kg) by creek and separated by land-side and river-side. Peach Island East shows significantly larger PCBs concentrations compared to all other creeks.

Organic pollutants and metals gradients from tide gates

Sediment samples (6 to 9) were taken from increasing distances towards the river and landward from each tide gate. A log-linear model was fitted to determine if concentrations moving away from a tide gate have positive or negative slopes for PCBs, OCPs, and metals. The linear model is given by:

Log y = α + βd (2)

Where d is the distance from the tide gate.

The model was fitted separately for each creek and for all creeks combined. The first finding is that all metals have negative slopes moving away from tide gates. Only Cr, Hg, Mn, and Ni have significant negative slopes (p<0.05) while Pb and Zn are only slightly significant (p<0.10). In contrast, concentrations of PCBs and OCPs showed no significant slopes moving away from tide gates (Figure 7).

Figure 7 Change in Cr, Hg, Mn, and Ni concentrations by creek with distance from the tide gate. (DP: ♦, Depyster; ER: ■, East Riser; LS: ▲, Losen Slote; MC: ×, Moonachie; WR: *, West Riser; PN: ●, Peach Island North.)

Discussion

When comparing metal concentration between geographic locations it’s important to normalize by particle size in order to remove particle size distribution effects in the comparisons between samples. In our case the overriding particle fractions in surficial sediments are clay and fine silts (>50%)(NCSS, 2015 and through out , this small area (5x5 Km) particle size distribution closely resembles the texture of the two dominant soils (Westbrook and Ipswich; NCSS, 2015). Studies that have looked at the relationship between heavy metals, river mile, particle size and organic matter have found that the best predictor for metal concentration in the Meadowlands was organic matter (Konsevick and Bragin 2010). Given that the amount of organic matter content in Meadowlands tidal creek sediments is fairly constant (~ 12.3 % (SD ± 3, N=15) (MERI, 2016), we

assume that sediments in all creeks are sufficiently similar and any difference in pollutant concentration is most likely due to levels of contamination.

Sediments were enriched with cadmium, mercury and chromium. Historical District wide Cadmium concentration decreased three fold between 1988 and 2003 (Konsevick and Bragin 2010). They are still however three times greater than average Cd concentrations reported for salt marshes in Europe and North (Williams et al, (1994). It is most likely that sediments in the estuary continue to be enriched with Cadmium from waste disposal and industrial emissions but at much lower rates.

Mercury has long been recognized as one of the most problematic contaminants in the Hackensack estuary (Lodge et al, 2015)2 . We found that the average surficial sediment concentration in tidal creeks was 13.4 ug/Kg and as a high 100. According to Weis et al (2005) concentrations of Hg, Cd, Hg, Cr, Cu, and Zn peak at depths of 12-16 cm. At these depths Hg can reach up to 1000 ug/Kg. These high levels reflect a legacy of pollution from the 1960’s and 1970’s. Approximately 160 tons of mercury were dumped into Berry’s Creek from site A between 1929 and 1974 (USEPA. 2006). There are also known non-point sources of mercury in the form of fly ash from coal burning plants that are contributing Mercury (Adriano et al. 1980). Mercury in the Meadowlands continuous to be present in the water column where levels in the order of 25-52 ug/Kg were measured from suspended particles and sediment traps in 2003-2004 (Weis et al 2005) exceeding the “effects range median” (ER-M) criteria (Long and Morgan, 1990)3. This suggests that active Hg contamination may still be taking place from the resuspension of legacy sediments or even new sources.

Chromium concentrations averaged 154.g ug/Kg (SD± 246.3). Konsevick and Bragin (2010) showed similar levels (130 ug/Kr). Chromium levels were consistently higher in the main channel of the Hackensack River compared to the creek. During most of the 20th century, locations along the Hackensack River (preferentially in Hudson County) were the center for chromate manufacturing facilities with a resulting 2 to 3 million tons of Cr residues distributed as fill material along the Meadowlands estuary (Burke 1991, Goeller 1989)). Concentrations as high as 2,420 ug/Kg have been reported by (Weis et al 2005). Konsevick and Bragin (2010) measured a 63% decrease in surficial Cr concentrations from 21 locations throughout the estuary between 1988 and 2003.

Lead concentrations in tidal creeks averaged 169 ug/Kg (SD±86.7). Nearby soil profiles (Pedon No. 15N068. NCSS, 2015) show similar values and deeper in the profile (22-48 cm) concentrations of Pb peak of 459.9 ug/Kg (Weis et al, 2005). Levels were similar to concentrations found in forest floors of northeastern Atlantic states (Johnson et al. 1982). The low dispersion around the mean of Pb concentrations may be explained by a

2 Lodge et al 2015. Contamination assessment and reduction project (Carp) summary report. Hudson River Foundation. 3 Long and Morgan 1990. Technical memorandum NOS OMA 52. NOAA., Seattle, Washington. 19

wide spread aerial deposition of this element. The main source of Pb in the 1980’s was most likely from the combustion of Pb-containing fuel used as an anti-knock additive in gasoline. Today’s most likely source of Pb is aerial deposition from nearby coal fired power plants (Feng et al. 2010). The average concentration of Zinc in tidal creeks was 466.9 ug/kg (SD±338.9) which is almost twice the Zn concentration found in nearby marsh surfaces (Pedon No. 15N068 NCSS, 2015) but similar to reference sites from Europe and North America (Williams et al 1994). Pb and Zn clustered along the PC2 axis suggesting a common aerial deposition source that would also have to include the wear of automobile tires and road dust (Varma and Doty 1980). Spikes in Mn in western creeks are connected to a few outliers and when outliers were removed, the average concentration of Manganese among creeks was not different to uncontaminated soils (~250 mg/kg) (Moore 1991; Reimer 1988).

The levels of PCB concentration in sampled creeks are similar to the lower levels found in some of the world’s renown PCBs hot spots such as the Hudson River and the Hudson-Raritan Bay system which range from 286 to 1,950 µg/kg (Fowler 1990). Concentrations of PCB’s were higher in the western creeks and overall no differences were observed from either side of the tide gate. This complicates discriminating local sources of PCB’s from Hudson River sources that affect the entire region (Citation). The most common OCP’s were DDT and BHC and their degradation products and isomers. DDT was widely used in mosquito control and later replace or co-applied with Lindane (99.9 % Gamma-Hexachlorocyclohexane) (Davidson 1947). DDD is the degradation product of DDT and is found at higher concentrations than the original compound. Greater concentrations of DDT would be expected deeper in the muck where degradation rates are slower (Aislabie et al. 1997). The most abundant BHC isomer was Gamma-Hexachlorocyclohexane which has the greatest biocide effect compared to the other BHC isomers (ATSDR 2005). The production of one ton of technical grade Lindane (99.9 % Gamma-Hexachlorocyclohexane) produces about 6-10 tons of alpha, beta and delta “waste isomers” (Li 1999). We found that the most common isomer is not the insecticidal gamma-BHC, but the “waste isomer” delta-BHC suggesting that BHC residues found in creeks may have their origin from former facilities that recycled BHC as waste products.

Organic pollutants and heavy metals in western creeks connected to Berry’s creek are several times higher than eastern creeks. The historical gradient between the high levels of contaminants in the western creeks along industrial land uses does not seem to have being exported in massive quantities to the eastern creeks by the surge. Data shows that the contaminant profile and levels found in western creeks are different (lower) from eastern creeks and remained this way after Sandy.

Finally, data shows that there are significant metal gradients around tide gates. Metal concentrations are significantly higher close to tide gate structures. These same gradients were not observed for PCB’s. Solubility 20

and therefore mobility of organic pollutants like PCB’s depends mainly on their distribution coefficients and differences in Kow coefficients among PCB congeners may account for the lack of concentration gradients around tide gates. Tide gates encourage the concentration of heavy metals and as such may play a role in their distribution across the estuary.

Conclusions

Sediments were most enriched with cadmium, mercury and chromium. Mercury in the estuary continuous to be present in the water column. This uggests that active Hg contamination may still be taking place from the resuspension of legacy sediments or even new sources. Chromium levels were consistently higher in the main channel of the Hackensack River compared to the creeks; a legacy of chromate manufacturing facilities from the 19th. Century. Pb levels were similar to concentrations found in forest floors of northeastern Atlantic and the average concentration of Zinc was similar to reference sites from Europe and North America. Concentrations of PCB’s were higher in the western creeks and overall no differences were observed from either side of tide gates. The most common OCP’s were the degradation products of the original DTT and Lindane (BHC) used for mosquito control. This shows chlorinated organic pollutants are undergoing degradation by microorganism when there is oxygen and through abiotic process from the electron dense reducing environments.Massive export of contaminants from western to eastern creeks due to Super Storm Sandy’ sea surge was not apparent and finally, tide gates encourage the concentration of heavy metals around these structures and as such play a role in their distribution across the estuary.

Acknowledgments

The authors thank Yefim Levinsky for the chemical analysis as well as Sal Kojak for collecting the GPS locations and the MERI Geographical Information System group for making the maps. Inputs from Michael Stepowyj and Sandy Speers are well appreciated. This research was supported by Meadowlands Environmental Research Institute and the New Jersey Meadowlands Commission (now the New Jersey Sports and Exhibition Authority).

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