Microplastic abundance in gull nests in relation to urbanization.

Human activity and urbanization are having profound effects on natural landscapes and ecosystems. The presence and persistence of human-made materials such as microplastics can have major impacts on the health of organisms in both marine and terrestrial environments. We quantified microplastics in herring gull (Larus argentatus) and great black-backed gull (Larus marinus) nests at three colonies in the northeast United States that varied in their degree of urbanization: Jamaica Bay (JB) in New York City, Youngs Island (YI) on Long Island, New York, and Tuckernuck Island (TN) in Massachusetts. Nests in urban colonies contained a higher proportion of microplastics than those in the more remote colony. Our results link urbanization with microplastic accumulation in coastal environments and suggest that assessing microplastics in seabird nests could provide a means of evaluating microplastics encountered by seabirds and other coastal marine animals.

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 Island's south shore lagoonal system, achieved notoriety when their polluted conditions were alluded to in a report of the US President's 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.

Determination of steroid estrogens in wastewater by immunoaffinity extraction coupled with HPLC-electrospray-MS.

A new method, based on immunoaffinity extraction coupled with liquid chromatography/electrospray mass spectrometry (LC/ESI-MS) is described for the determination of the steroid estrogens beta-estradiol (E2), estrone (E1), and alpha-ethynylestradiol (E2) in wastewater. The use of highly selective immunosorbents in sample preparation prior to analysis allows the removal of interfering sample matrix compounds present in the wastewater extracts that would otherwise cause severe ionization suppression of the estrogens during the electrospray process. In addition, immunoextraction removes much of the isobaric noise from the selected ion monitoring chromatograms, increasing the signal-to-noise ratios for analytes, and contributing to the low detection limits (0.18 and 0.07 ng/L for E2 and E1, respectively) achieved by the current method. The method was applied to analysis of estrogens in two wastewater effluents. Recoveries of E2 and E1 were excellent (>90%), while the nonimmunogen (but structurally related) analyte EE2 was not retained (recovery <2%) from effluent extracts by the immunosorbent. This illustrates the extreme selectivity of the immunoextraction purification step. Precision of the method was high, with relative standard deviations below 5%. Concentrations of E2 in wastewater varied from 0.77 to 6.4 ng/L, while concentrations of E1 were greater (1.6-18 ng/L).

Distribution and fate of neutral alkylphenol ethoxylate metabolites in a sewage-impacted urban estuary.

The distribution and fate of neutral metabolites of the alkylphenol ethoxylate (APEO) surfactants in an urbanized estuarine environment were examined utilizing a recently developed, highly sensitive LC-MS method. Results indicated that short ethoxyl-chain APEOs and alkylphenols (APs) were present in surficial sediments throughout the estuary at concentrations roughly correlated to the organic carbon content of the sediment and that the APEO mixture was dominated by nonylphenol ethoxylate (NPEOs) metabolites (0.05-30 microg/g), with lesser amounts of octylphenol ethoxylate metabolites (OPEOs)(<0.005-0.09 microg/ g) and halogenated nonylphenols (<0.001-0.03 microg/g). NPEO metabolites in surface water (0.22-1.05 microg/L) were also present at higher concentrations than OPEO metabolites (0.007-0.040 microg/L). APEO metabolite concentrations in both sediment and water showed a strong correlation with conventional sewage tracers, affirming a wastewater source of these contaminants. APEO distributions in surface waters within the estuary could be explained by a combination of post-discharge degradation and mixing with a seawater end-member enriched in OPEO metabolites. Measured in situ Koc values of APEO metabolites were comparable to previously reported values derived from field experiments but higher than Kow and Koc values derived from laboratory experiments. Results from the present work indicate that the fate of APEO metabolites entering the estuarine environment through discharge of wastewater is directed primarily by scavenging onto particles and subsequent burial in sediments, degradation during residence in the water column, and transport out of the estuary through advective and dispersive processes.

Presence of morphine and morphine-6-glucuronide in the marine mollusk Mytilus edulis ganglia determined by GC/MS and Q-TOF-MS. Starvation increases opiate alkaloid levels.

Morphine and morphine-6-glucuronide, a morphine metabolite, have been identified and quantified in Mytilus edulis pedal ganglia at a level of 2.67+/-0.44 and 0.98+/-0.14 ng/ganglia, respectively by high performance liquid chromatography coupled to electrochemical detection. These opiate alkaloids were further identified by both gas-chromatography mass spectrometry and nanoflow electrospray ionization double quadrupole orthogonal acceleration Time of Flight mass spectrometry. In animals that were starved, the morphine level rose to 6.38+/-0.88 ng/ganglion and the morphine 6-glucoronide rose to a level of 23.0+/-3.2 ng/ganglion after 30 days. These studies demonstrate that opiate alkaloids are present as naturally occurring signal molecules whose levels respond to stress, i.e., starvation. Opiate alkaloids were not found in the animal's incubation media or food, demonstrating their synthesis occurred in the respective tissue. These new method of opiate alkaloid detection, conclusively proves that morphine and morphine-6-glucuronide are present in animal tissues.

Identification of morphine in the adrenal medullary chromaffin PC-12 cell line.

Morphine was identified in the adrenal medulla chromaffin PC-12 cell line by reversed-phase HPLC, following liquid and solid extraction. The morphine corresponding HPLC fractions (1.746+/-0.615 ng of morphine/million cells) were further analyzed by gas chromatography-mass spectrometry and found to be identical to synthetic morphine. Furthermore, using primers derived from the human neuronal mu 1 opiate receptor, we used RT-PCR to detect expression of mu transcripts from this cell line. The transcript was absent. The study conclusively proves morphine, but not a mu opiate receptor, is constitutively expressed in the adrenal medulla chromaffin PC-12 cell line.

Analysis of alkylphenol ethoxylate metabolites in the aquatic environment using liquid chromatography-electrospray mass spectrometry.

A quantitative method is described for the analysis of the metabolites of alkylphenol ethoxylate (APEO) surfactants in estuarine water and sediment samples using reversed-phase high-performance liquid chromatography with electrospray mass spectrometry detection. Nonyl- and octylphenols, nonyl- and octylphenol mono-, di-, and triethoxylates, halogenated nonylphenols, and nonylphenol ethoxycarboxylates were concentrated from water samples using a C18 solid-phase extraction procedure. A novel, continuous-flow, high-temperature, sonicated extraction system was developed to isolate APEO metabolites from sediment samples. Quantitative LC-MS was performed in the negative ion mode for nonylphenols, octylphenols, and halogenated nonylphenols and in the positive ion mode for nonyl- and octylphenol ethoxylates using selected ion monitoring with isotopically labeled surrogate standards. Recoveries for sediment and water analyses ranged between 78 and 94%, and detection limits for APEO metabolites were between 1 and 20 pg injected on column. This is a significant improvement over previously reported methods. Suppression of analyte response was encountered in the presence of matrix components in sediment samples, but this effect was eliminated by careful selection of surrogate and internal standards. Individual APEO metabolite concentrations of 1-320 ng/L and 5-2000 ng/g are reported for water and sediment samples, respectively, from Jamaica Bay, NY.

Ascaris suum, an intestinal parasite, produces morphine.

The parasitic worm Ascaris suum contains the opiate alkaloid morphine as determined by HPLC coupled to electrochemical detection and by gas chromatography/mass spectrometry. The level of this material is 1168 +/- 278 ng/g worm wet weight. Furthermore, Ascaris maintained for 5 days contained a significant amount of morphine, as did their medium, demonstrating their ability to synthesize the opiate alkaloid. To determine whether the morphine was active, we exposed human monocytes to the material, and they immediately released nitric oxide in a naloxone-reversible manner. The anatomic distribution of morphine immunoreactivity reveals that the material is in the subcuticle layers and in the animals' nerve chords. Furthermore, as determined by RT-PCR, Ascaris does not express the transcript of the neuronal mu receptor. Failure to demonstrate the expression of this opioid receptor, as well as the morphine-like tissue localization in Ascaris, suggests that the endogenous morphine is intended for secretion into the microenvironment.