Bruce J. Brownawell

Occurrence, distribution and partitioning of nonionic surfactants and pharmaceuticals in the urbanized Long Island Sound Estuary (NY)

This work deals with the environmental distribution of nonionic surfactants (nonylphenol and alcohol ethoxylates), their metabolites (NP, nonylphenol; NPEC, nonylphenol ethoxycarboxylates; and PEG, polyethylene glycols) and a selection of 64 pharmaceuticals in the Long Island Sound (LIS) Estuary which receives important sewage discharges from New York City (NYC). Most target compounds were efficiently removed (>95%) in one wastewater treatment plant monitored, with the exception of NPEC and some specific drugs (e.g., hydrochlorothiazide). Concentrations of surfactants (1.4-4.5 μg L(-1)) and pharmaceuticals (0.1-0.3 μg L(-1)) in seawater were influenced by tides and sampling depth, consistent with salinity differences. Surfactants levels in suspended solids samples were higher than 1 μg g(-1), whereas only most hydrophobic or positively charged pharmaceuticals could be found (e.g., tamoxifen, clarithromycin). Maximum levels of target compounds in LIS sediments (PEG at highest concentrations, 2.8 μg g(-1)) were measured nearest NYC, sharply decreasing with distance from major sewage inputs.

Transformation Products and Human Metabolites of Triclocarban and Triclosan in Sewage Sludge Across the United States

Removal of triclocarban (TCC) and triclosan (TCS) from wastewater is a function of adsorption, abiotic degradation, and microbial mineralization or transformation, reactions that are not currently controlled or optimized in the pollution control infrastructure of standard wastewater treatment. Here, we report on the levels of eight transformation products, human metabolites, and manufacturing byproducts of TCC and TCS in raw and treated sewage sludge. Two sample sets were studied: samples collected once from 14 wastewater treatment plants (WWTPs) representing nine states, and multiple samples collected from one WWTP monitored for 12 months. Time-course analysis of significant mass fluxes (α = 0.01) indicate that transformation of TCC (dechlorination) and TCS (methylation) occurred during sewage conveyance and treatment. Strong linear correlations were found between TCC and the human metabolite 2′-hydroxy-TCC (r = 0.84), and between the TCC-dechlorination products dichlorocarbanilide (DCC) and monochlorocarbanilide (r = 0.99). Mass ratios of DCC-to-TCC and of methyl-triclosan (MeTCS)-to-TCS, serving as indicators of transformation activity, revealed that transformation was widespread under different treatment regimes across the WWTPs sampled, though the degree of transformation varied significantly among study sites (α = 0.01). The analysis of sludge sampled before and after different unit operation steps (i.e., anaerobic digestion, sludge heat treatment, and sludge drying) yielded insights into the extent and location of TCC and TCS transformation. Results showed anaerobic digestion to be important for MeTCS transformation (37–74%), whereas its contribution to partial TCC dechlorination was limited (0.4–2.1%). This longitudinal and nationwide survey is the first to report the occurrence of transformation products, human metabolites, and manufacturing byproducts of TCC and TCS in sewage sludge.

Hypoxia depresses CYP1A induction and enhances DNA damage, but has minimal effects on antioxidant responses in sheepshead minnow (Cyprinodon variegatus) larvae exposed to dispersed crude oil

The growing incidence of hypoxic regions in coastal areas receiving high volumes of anthropogenic discharges requires more focused risk assessment of multiple stressors. One area needing further study is the combined effect of hypoxia and oil exposure. This study examined the short-term sublethal effects of co-exposure to hypoxia and water accommodated fractions (WAF) and chemically enhanced WAFs (CEWAFs) of Southern Louisiana Crude oil on detoxification, antioxidant defenses and genotoxicity in early life stage sheepshead minnow (Cyprinodon variegatus). CYP1A induction (evaluated by measuring EROD activity), activity of a number of key antioxidant enzymes (GST, GR, GPx, SOD, CAT, and GCL), levels of antioxidants (tGSH, GSH, and GSSG), evidence of lipid peroxidation (evaluated using the TBARS assay), and DNA damage (evaluated using the comet assay) provided a broad assessment of responses. Contaminant detoxification pathways induced by oil exposure were inhibited by co-exposure to hypoxia, indicating a maladaptive response. The interactive effects of oil and hypoxia on antioxidant defenses were mixed, but generally indicated less pronounced alterations, with significant increases in lipid peroxidation not observed. Hypoxia significantly enhanced DNA damage induced by oil exposure indicating the potential for significant deleterious effects post exposure. This study demonstrates the importance of considering hypoxia as an enhanced risk factor in assessing the effects of contaminants in areas where seasonal hypoxia may be prevalent.

Occurrence, temporal variation, and estrogenic burden of five parabens in sewage sludge collected across the United States

Five parabens used as preservatives in pharmaceuticals and personal care products (PPCPs) were measured in sewage sludges collected at 14 U.S. wastewater treatment plants (WWTPs) located in nine states. Detected concentration ranges (ng/g, dry weight) and frequencies were as follows: methyl paraben (15.9 to 203.0; 100%), propyl paraben (0.5 to 7.7; 100%), ethyl paraben (<0.6 to 2.6; 63%), butyl paraben (<0.4 to 4.3; 42%) and benzyl paraben (<0.4 to 3.3; 26%). The estrogenicity inherent to the sum of parabens detected in sewage sludge (ranging from 10.1 to 500.1pg/kg 17β-estradiol equivalents) was insignificant when compared to the 106-times higher value calculated for natural estrogens reported in the literature to occur in sewage sludge. Temporal monitoring at one WWTP provided insights into temporal and seasonal variations in paraben concentrations. This is the first report on the occurrence of five parabens in sewage sludges from across the U.S., and internationally, the first on temporal variations of paraben levels in sewage sludge. Study results will help to inform the risk assessment of sewage sludge destined for land application (biosolids).

Partitioning of alcohol ethoxylates and polyethylene glycols in the marine environment: Field samplings vs laboratory experiments

Nowadays, alcohol ethoxylates (AEOs) constitute the most important group of non-ionic surfactants, used in a wide range of applications such as household cleaners and detergents. Significant amounts of these compounds and their degradation products (polyethylene glycols, PEGs, which are also used for many other applications) reach aquatic environments, and are eliminated from the water column by degradation and sorption processes. This work deals with the environmental distribution of AEOs and PEGs in the Long Island Sound Estuary, a setting impacted by sewage discharges from New York City (NYC). The distribution of target compounds in seawater was influenced by tides, consistent with salinity differences, and concentrations in suspended solid samples ranged from 1.5 to 20.5 μg/g. The more hydrophobic AEOs were mostly attached to the particulate matter whereas the more polar PEGs were predominant in the dissolved form. Later, the sorption of these chemicals was characterized in the laboratory. Experimental and environmental sorption coefficients for AEOs and PEGs showed average values from 3607 to 164,994 L/kg and from 74 to 32,862 L/kg, respectively. The sorption data were fitted to a Freundlich isotherm model with parameters n and log KF between 0.8-1.2 and 1.46-4.39 L/kg, respectively. AEO and PEG sorptions on marine sediment were also found to be mostly not affected by changes in salinity.

What history reveals about Forge River pollution on Long Island, New York’s south shore

Fifty years ago, the Forge River and Moriches Bay, of Long Islands south shore lagoonal system, achieved notoriety when their polluted conditions were alluded to in a report of the US Presidents Science Advisory Committee (1965). The Woods Hole Oceanographic Institution investigated the bay throughout the 1950s, identifying duck farming as the cause of objectionable, highly contaminated conditions of these waters. Much has changed: duck farming declined; the river was dredged to remove polluted sediments, improve navigation; and barrier island inlets stabilized. Yet, the river remains seasonally eutrophic. Why? This paper reviews what occurred in the Forge River watershed. While governments aggressively curtailed the impacts of duck pollution, they failed to manage development and sewage pollution. The Forge experience indicates that watershed management is a continuing governmental responsibility as development accelerates. Otherwise, we will always be looking for that instantaneous remediation that is usually not affordable and is socially contentious.

SIMULATIONS OF TRANSIENT PESTICIDE CONCENTRATIONS IN LONG ISLAND SOUND FOR LATE SUMMER 1999 WITH A HIGH RESOLUTION COASTAL CIRCULATION MODEL

Abstract Results for hindcast simulations are presented for the transient concentration distributions in Long Island Sound for the pesticides malathion, resmethrin and sumithrin for the period August 1, 1999 through October 19, 1999. The high resolution of the simulations provide information concerning the detailed spatial patterns in time varying concentration distributions that are dependent on the distribution of pesticide loadings around the perimeter of the basin. Plume concentrations attenuate very rapidly with distance from the coast to below 0.001 μg/L; high concentrations are detected only in confined coastal embayments and regions immediately adjacent to the coast. The decay rates used in the simulations have a strong influence on the concentration fields. Concentrations in plumes for pesticides dispersing into the western Sound from the East River also attenuate rapidly with distance from the East River.

Comparison of wastewater-associated contaminants in the bed sediment of Hempstead Bay, New York, before and after Hurricane Sandy

Changes in bed sediment chemistry of Hempstead Bay (HB) have been evaluated in the wake of Hurricane Sandy, which resulted in the release of billions of liters of poorly-treated sewage into tributaries and channels throughout the bay. Surficial grab samples (top 5cm) collected before and (or) after Hurricane Sandy from sixteen sites in HB were analyzed for 74 wastewater tracers and steroid hormones, and total organic carbon. Data from pre- and post-storm comparisons of the most frequently detected wastewater tracers and ratios of steroid hormone and of polycyclic aromatic hydrocarbon concentrations indicate an increased sewage signal near outfalls and downstream of where raw sewage was discharged. Median concentration of wastewater tracers decreased after the storm at sites further from outfalls. Overall, changes in sediment quality probably resulted from a combination of additional sewage inputs, sediment redistribution, and stormwater runoff in the days to weeks following Hurricane Sandy.

Fate of methoprene in temperate salt marsh ditches following aerial applications

Aerial applications of liquid methoprene are used in salt marshes to control mosquitoes by preventing adult emergence. Despite concern about toxicity to non-target organisms, little is known about environmental concentrations after applications, nor methoprenes persistence in salt marsh environments. Aqueous and sediment samples were collected from two marshes receiving weekly applications. Aqueous samples were collected as early as 30u202fmin after applications and as long as nine days afterwards; sediment samples were taken within hours of application and as long as 19u202fdays post-application. Use of time-of-flight liquid chromatography - mass spectral analysis allowed for ultra-low detection limits (0.5u202fng/L) in water samples. The data show loss of nearly all methoprene from 1u202fm deep marsh ditches within 1u202fday and presence but not accumulation of methoprene in marsh sediments despite repeated applications. Methoprene concentrations observed in salt-marsh mosquito ditches were below those found to be of toxicological significance in other studies.

Distribution and diagenetic fate of synthetic surfactants and their metabolites in sewage-impacted estuarine sediments

Surfactants are high production volume chemicals used in numerous domestic and industrial applications and, after use, the most abundant organic contaminants in wastewater. Their discharge might jeopardize the receiving aquatic ecosystems, including sediments, where they tend to accumulate. This is the first comprehensive study on their distribution and fate in this environmental compartment as we performed simultaneous analysis of the three main classes of surfactants (anionic: LAS; nonionic: NPEO and AEO; cationic: DTDMAC, DADMAC, BAC, and ATMAC) and some of their transformation products (SPC, NP, NPEC, and PEG). To account for spatial and time trends, surface sediments and dated cores were collected from Jamaica Bay, a heavily sewage-impacted estuary in New York City. The concentrations of surfactants in surface sediments were between 18 andu202f>u202f200u202fμgu202fg-1 and showed slight variation (<10%) over different sampling years (1998, 2003 and 2008). Cationic surfactants were found at the highest concentrations, with DTDMAC accounting for between 52 and 90% of the total sum of target compounds. Vertical concentration profiles in dated cores from the most contaminated station, in the vicinity of the biggest local sewage treatment plant (STP), indicated two sub-surface surfactant peaks in the mid-1960s (469u202fμgu202fg-1) and late 1980s (572u202fμgu202fg-1) coinciding with known STP upgrades. This trend was observed for most target compounds, except for DADMAC, C22ATMAC, and PEG, which showed a continuous increase towards the top of the cores. In-situ degradation was studied by comparing sediment core samples taken 12 years apart (1996 and 2008) and revealed a net decrease in PEG and specific surfactants (BAC, ATMAC, NPEO, and AEO) accompanied by growing concentrations of metabolites (SPC, NP, and NPEC). DTDMAC, DADMAC, and LAS, however, remained stable over this period, suggesting recalcitrant behavior under the anaerobic conditions in Jamaica Bay sediments.nnnMAIN FINDINGnChronology of major synthetic surfactants are illustrated in the dated sediment cores, as well as their different diagenetic fates.