New Jersey Water Science Center

Concentrations and Loads of Organic Compounds and Trace Elements in Tributaries to Newark and Raritan Bays, New Jersey

Prepared for the New Jersey Toxics Reduction Workplan for NY-NJ Harbor Ambient Monitoring of Loading to Major Tributaries at Head-of-Tide Study I-C

By Timothy P. Wilson and Jennifer L. Bonin

Scientific Investigations Report 2007-5059

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Abstract

A study was undertaken to determine the concentrations and loads of sediment and chemicals delivered to Newark and Raritan Bays by five major tributaries: the Raritan, Passaic, Rahway, Elizabeth, and Hackensack Rivers. This study was initiated by the State of New Jersey as Study I-C of the New Jersey Toxics Reduction Workplan for the New York-New Jersey Harbor, working under the NY-NJ Harbor Estuary Program (HEP) Contaminant Assessment and Reduction Program (CARP). The CARP is a comprehensive effort to evaluate the levels and sources of toxic contaminants to the tributaries and estuarine areas of the NY-NJ Harbor, including Newark and Raritan Bays. The Raritan and Passaic Rivers are large rivers (mean daily discharges of 1,189 and 1,132 cubic feet per second (ft3/s), respectively), that drain large, mixed rural/urban basins. The Elizabeth and Rahway Rivers are small rivers (mean daily discharges of 25.9 and 49.1 ft3/s, respectively) that drain small, highly urbanized and industrialized basins. The Hackensack River drains a small, mixed rural/urban basin, and its flow is highly controlled by an upstream reservoir (mean daily discharge of 90.4 ft3/s). These rivers flow into urbanized estuaries and ultimately, to the Atlantic Ocean.

Each of these tributaries were sampled during two to four storm events, and twice each during low-flow discharge conditions. Samples were collected using automated equipment installed at stations adjacent to U.S. Geological Survey streamflow-gaging stations near the heads-of-tide of these rivers. Large-volume (greater than 50 liters of water and a target of 1 gram of sediment), flow-weighted composite samples were collected for chemical analysis using filtration to collect suspended particulates and exchange resin (XAD-2) to sequester dissolved contaminants. Composite whole-water samples were collected for dissolved polycyclic aromatic hydrocarbons (PAH) and for trace element analysis. Additional discrete grab samples were collected throughout each event for trace-element analysis, and multiple samples were collected for suspended sediment (SS), particulate carbon (POC), and dissolved organic carbon (DOC) analysis. The suspended sediment and exchange resin were analyzed for 114 polychlorinated biphenyls (PCBs, by US EPA method 1668A, modified), seven 2,3,7,8-substituted chlorinated dibenzo-p-dioxins (CDD) and 10 dibenzo-p-difurans (CDF) (by US EPA method 1613), 24 PAHs (by low-resolution isotope dilution/mass-spectral methods), 27 organo-chlorine pesticides (OCPs) (by high resolution isotope dilution/mass-spectral methods), and the trace elements mercury (Hg), methyl-mercury (MeHg), lead (Pb), and cadmium (Cd). Isotope dilution methods using gas chromatography and high-and low-resolution mass spectral (GC/MS) detection were used to accurately identify and quantify organic compounds in the sediment and water phases. Trace elements were measured using inductively coupled plasma-mass spectrometry and cold-vapor atomic fluorescence spectrometry methods.

The loads of sediment, carbon, and chemicals were calculated for each storm and low-flow event sampled. Because only a few storm events were sampled, yearly loads of sediment were calculated from rating curves developed using historical SS and POC data. The average annual loads of sediment and carbon were calculated for the period 1975-2000, along with the loads for the selected water years being modeled as part of the New York New Jersey Harbor Estuary Program CARP. Comparison of loads calculated using the rating curve method to loads measured during the sampled storm events indicated that the rating curve method likely underpredicts annual loads.

Average annual loads of suspended sediment in the tributaries were estimated to be 395,000 kilograms per year (kg/yr) in the Hackensack River, 417,000 kg/yr in the Elizabeth River, 882,000 kg/yr in the Rahway River, 22,700,000 kg/yr in the Passaic River, and 93,100,000 kg/yr in the Raritan River. Average annual loads of POC were estimated to range from 14,400 kg in the Elizabeth River to 866,000 kg in the Raritan River. DOC ranged from 89,000 kg/yr in the Elizabeth River to 4,260,000 kg/yr in the Passaic River. These sediment loads and the average chemical concentrations measured in this study were used to estimate the loads of organic compounds and trace elements for the average year and for selected water years.

The highest average concentrations of sediment-bound total PCBs were found in the Elizabeth River (2,460 ng/g) and the lowest in the Raritan River (44 ng/g). The highest average concentrations of dissolved total PCBs were also found in the Elizabeth River (5,050 pg/L), while the lowest were found in the Hackensack River (740 pg/L). Average annual loads of total PCBs (sum of all congeners measured) in the tributaries were estimated to be 74 g/yr in the Hackensack River, 440 g/yr in the Rahway River, 1,150 g/yr in the Elizabeth River, 5,000 g/yr in the Raritan River, and 7,200 g/yr in the Passaic River. From 47 to 90 percent of the total load was estimated to be associated with the particulate phase. The New Jersey State Surface Water Quality Criteria (NJSWQC) for Human Health was exceeded by the average concentration in all the rivers and the aquatic chronic criteria was exceeded by the average concentration in the Elizabeth and individual samples in the Passaic and Rahway Rivers.

The highest average concentrations of sediment-bound total CDD plus CDFs were found in the Elizabeth River (28.9 ng/g) and the lowest in the Hackensack River (5.6 ng/g). The CDD and CDF congeners were detected in the suspended sediment from all the tributaries, although the most toxic congener (2,3,7,8-TCDD) was detected only occasionally in the Passaic, Elizabeth, and Raritan Rivers and at very low concentrations. The dominant CDD and CDF compounds in all the rivers were the octachloro-dioxin and octachloro-difuran congeners. The average annual total loads of 2,3,7,8-substituted dioxins plus furans were estimated to be 2.2 g/yr in the Hackensack River, 10 g/yr in the Rahway River, 12 g/yr in the Elizabeth River, 260 g/yr in the Passaic River, and 1,070 g/yr in the Raritan River. The higest average toxicity concentrations represented by toxic equivalencies (TEQs), of dioxins, furans, and dioxin-like PCBs was measured in the Elizabeth River (201 pg/g), and the lowest in the Raritan River (20 pg/g). Average annual total toxicity loads from CDD, CDF, and co-planar PCBs (as TEQ) were estimated to be 11 milligrams per year (mg/yr) in the Hackensack River, 56 mg/yr in the Rahway River, 84 mg/yr in the Elizabeth River, 870 mg/yr in the Passaic River, and 1,800 mg/yr in the Raritan River. The contribution to the total TEQ load contributed by dioxin-like PCBs ranged from 18 to 33 percent.

Average concentrations of sediment-bound and dissolved total PAH compounds were generally largest in the Elizabeth River and the lowest in the Hackensack and Raritan Rivers. Average annual loads of total PAHs (sum of all sediment-bound and dissolved PAH compounds measured) were estimated to be 15 kg/yr in the Hackensack River, 69 kg/yr in the Rahway River, 280 kg/yr in the Elizabeth River, 1,000 kg/yr in the Passaic River, and 1,400 kg in the Raritan River. Sediment-bound PAHs dominated (71 percent) the total PAH load in the Raritan River while dissolved PAH compounds dominated (80 percent) the PAH load in the Elizabeth River. Dissolved PAH compounds comprise about 60 percent of the load in the Passaic, Rahway, and Hackensack Rivers. Sediment-bound PAHs and dissolved PAHs were dominated by the high molecular-weight (greater than 202 g per mole) compounds. Because of the small 1 to 2 Liter sample volumes used for analysis, and blank contamination, low concentrations of dissolved PAH could not be measured, resulting in some uncertainty and underestimation in the dissolved loads. Whole-water concentrations of several of the PAH compounds were found to exceed the NJSWQC in all of the rivers studied.

Average concentrations of sediment-bound total OCP compounds were generally highest in the Elizabeth River (1,170 ng/g) and the lowest were in the Raritan River (60 ng/g), while the highest dissolved concentrations were found in the Rahway River (9.5 ng/L) and the lowest were in the Raritan River (2.3 ng/L). Average annual loads of total OCPs (sum of all OCP compounds measured) were estimated to be 420 g/yr in the Hackensack River, 670 g/yr in the Elizabeth River, 1,100 g/yr in the Rahway River, 6,300 g/yr in the Passaic River, and 6,600 g/yr in the Raritan River. Between 40 and 74 percent of these compounds were associated with the particulate phase. The dominant compounds in suspended sediment were the DDT series (DDT, DDD, and DDE) and chlordane series. The dominant compounds in the dissolved phase were the chloradane series in the Rahway, Elizabeth and Hackensack Rivers, and the BHC series in the Passaic and Raritan Rivers. The NJSWQC for 4,4’-DDD, DDE, and DDT were exceeded in all the samples from the Rahway and Elizabeth Rivers, and occasionally in other river samples.

Average concentrations of total (whole-water) mercury and lead were highest in the Rahway River, while the average whole-water Cd concentration was highest in the Elizabeth River. Average annual loads of Hg were found to fall in the order: Hackensack River (.070 kg/yr) < Rahway River (1.3) < Elizabeth River (2.2) < Passaic River (8.0) < Raritan River (13). The average annual loads of Pb were found fall in the order: Hackensack River (20 kg/yr) < Rahway River (450) < Elizabeth River (1,800) < Passaic River (2,100) < Raritan River (3,400). Average annual loads of Cd were found to fall in the order: Hackensack River (0.26 kg/yr) < Rahway River (4.5) < Elizabeth River (17) < Raritan River (54) < Passaic River (88). A varying proportion of the metal loads were associated with the sediment phase. Generally, 76 to 98 percent of the Hg and Pb load was found to be associated with sediment, while between 34 and 79 percent was associated with sediment.


Contents

Abstract

Introduction

Purpose and Scope

Geochemical Cycling in Estuaries

Description of Sample Collection, Sample Analysis, and Methods for Calculating Concentrations

Concentrations of Organic Compounds and Trace Elements

Polychlorinated Biphenyls

Methods

Quality Assurance

Recovery of Internal Standards

Recovery of Field Surrogates

Contamination of Blanks and Data Censoring

Concentrations

Anomalous Concentrations

Relation of Whole-Water Concentrations to Water-Quality Criteria

Distribution Among Homologs

Concentrations During Stormflow and Low Flow

Sediment-Water Partitioning

Chlorinated Dioxins and Furans

Methods

Quality Assurance

Recovery of Internal Standards

Contamination of Blanks and Data Censoring

Concentrations

Anomalous Concentrations

Relation of Whole-Water Concentrations to Water-Quality Criteria

Relative Concentrations

Concentrations During Stormflow and Low Flow

Sources of Dioxins and Furans

Sediment Toxicity

Polycyclic Aromatic Hydrocarbons

Methods

Quality Assurance

Recovery of Internal Standards

Contamination of Blanks and Data Censoring

Aqueous Method Blanks

Aqueous Field Blanks

Filter Method Blanks

Filter Field Blanks

Concentrations

Anomolous Concentrations

Relation of Whole-Water Concentrations to Water-Quality Criteria

Sources for the Polycyclic Aromatic Hydrocarbon Compounds

Sediment-Water Partitioning

Organochlorine Pesticides

Methods

Quality Assurance

Recovery of Internal Standards

Contamination of Blanks and Data Censoring

Recovery of Field Surrogates

Concentrations

Relation of Whole-Water Concentrations to Surface-Water-Quality Criteria

Concentrations During Stormflow and Low Flow

Pesticide Degradation, Relative Concentrations of Metabolites, and Indicator Ratios

Sediment-Water Partitioning

Mercury, Cadmium, and Lead

Methods

Quality Assurance

Contamination of Blanks and Data Censoring

Concentrations

Relation of Whole-Water Concentrations to Surface-Water-Quality Criteria

Sediment-Water Partitioning

Predicted Concentrations in the Sediment and Water Phases

Tributary Loads of Sediment, Carbon, and Chemicals

Loads of Suspended Sediment and Carbon

Methods Used to Calculate Sediment and Carbon Loads

Concentrations and Loads of Particulates During Sampled Events

Annual Loads of Sediment Estimated From Historical Data

Annual Loads of Dissolved and Particulate Carbon Estimated From Historical Data

Tributary Loads of Chemicals

Methods Used to Estimate Chemical Loads

Polychlorinated Biphenyls

Dioxins, Furans, and Dioxin-Like Polychlorinated Biphenyls

Polycyclic Aromatic Hydrocarbons

Organochlorine Pesticides

Mercury, Cadmium, and Lead

Summary and Conclusions

Polychlorinated Biphenyls

Dioxin and Furans

Polycyclic Aromatic Hydrocarbons

Organochlorine Pesticides

Mercury, Cadmium, and Lead

Sediment and Carbon Loads

Chemical Loads

Acknowledgments

References Cited


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U.S. Department of the Interior, U.S. Geological Survey
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