Comparison of chemical contaminant measurements using CLAM, POCIS, and silicone band samplers in estuarine mesocosms.

Discrete water samples represent a snapshot of conditions at a particular moment in time and may not represent a true chemical exposure caused by changes in chemical input, tide, flow, and precipitation. Sampling technologies have been engineered to better estimate time-weighted concentrations. In this study, we consider the utility of three integrative sampling platforms: polar organic chemical integrative sampler (POCIS), silicone bands (SBs), and continuous, low-level aquatic monitoring (CLAM). This experiment used simulated southeastern salt marsh mesocosm systems to evaluate the response of passive (POCIS, SBs) and active sampling (CLAM) devices along with discrete sampling methodologies. Three systems were assigned to each passive sampler technology. Initially, all tanks were dosed at nominal (low) bifenthrin, pyrene, and triclosan concentrations of 0.02, 2.2, and 100 µg/L, respectively. After 28 days, the same treatment systems were dosed a second time (high) with bifenthrin, pyrene, and triclosan at 0.08, 8.8, and 200 µg/L, respectively. For passive samplers, estimated water concentrations were calculated using published or laboratory-derived sampling rate constants. Chemical residues measured from SBs resulted in high/low ratios of approximately 2x, approximately 3x, and 1x for bifenthrin, pyrene, and triclosan. A similar pattern was calculated using data from POCIS samples (~4x, ~3x, ~1x). Results from this study will help users of CLAM, POCIS, and SB data to better evaluate water concentrations from sampling events that are integrated across time. Integr Environ Assess Manag 2024;20:1384-1395. © 2024 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Assessment of the efficacy of six field cleaning protocols for hydrocarbon quantification.

The defensibility of field sampling data collected in support of natural resource damage assessments and other environmental investigations depends on rigorous quality assurance and control both in the field and laboratory. One important step in field procedures is the cleaning of sampling equipment between samples to minimize the carryover of contaminants. Large-scale sampling efforts during the Deepwater Horizon oil spill event have highlighted the importance of understanding how multiple equipment cleaning protocols affect interstation cross-contamination and the resulting chemical data quality. In this study, six field cleaning techniques were tested on metal sampling equipment using two different sediment types spiked with crude oil in order to understand their relative and absolute effectiveness in reducing chemical carryover. The complexity of the cleaning protocols ranged from a simple water and scrub brush application to protocols that included soap and/or solvent. In this study, percent residual hydrocarbon transfer, relative to total loading in sediments, never exceeded 0.032%. The least labor-intensive protocol, water and scrub brush application, had the highest potential for hydrocarbon transfer (0.011-0.032%). Statistical differences were observed among treatments, and it was found that protocols containing a solvent step were more effective than protocols without solvents. Depending on the data quality objectives, the differences may not be meaningful, and choosing a cleaning technique should be governed by health, safety, and environmental factors. The residual hydrocarbons measured after equipment cleanings for all techniques in this study were negligible when compared with other variables that occur during routine sampling and laboratory activities.

What Goes Up Must Come Down: Integrating Air and Water Quality Monitoring for Nutrients.

Excess nitrogen and phosphorus ("nutrients") loadings continue to affect ecosystem function and human health across the U.S. Our ability to connect atmospheric inputs of nutrients to aquatic end points remains limited due to uncoupled air and water quality monitoring. Where connections exist, the information provides insights about source apportionment, trends, risk to sensitive ecosystems, and efficacy of pollution reduction efforts. We examine several issues driving the need for better integrated monitoring, including: coastal eutrophication, urban hotspots of deposition, a shift from oxidized to reduced nitrogen deposition, and the disappearance of pristine lakes. Successful coordination requires consistent data reporting; collocating deposition and water quality monitoring; improving phosphorus deposition measurements; and filling coverage gaps in urban corridors, agricultural areas, undeveloped watersheds, and coastal zones.

Environmental PCBs in Guánica Bay, Puerto Rico: implications for community health.

Guánica Bay, located in southwestern Puerto Rico, has suffered oil spills and other pollution discharges since the 1960s. Previous research showed elevated concentrations of polychlorinated biphenyls (PCBs) in coral reef and sediment. This research examined PCB concentrations in sediment and fish. Sediment and fish sampling in the bay was facilitated by community members. This study identified the second highest reported PCB level (129,300 ng/g) in sediment in the USA. Fish samples also showed elevated concentrations (1623 to 3768 ng/g), which were higher than the thresholds of safe levels of PCBs in fish for human consumption. The alarmingly high concentration of PCBs calls for proactive community engagement to bring awareness about contamination of the bay and more extensive sampling to test for the concentration of PCBs in seafood and the people of Guánica. This study also underscores the value of the involvement of local communities during sampling design aimed at identifying hot spots of contaminants.

Chemical contaminants in surficial sediment in Coral and Fish Bays, St. John, U.S. Virgin Islands.

Land based sources of pollution have the potential to negatively impact coral reef ecosystems. Many coral systems, including environmentally sensitive marine protected areas, do not have assessments of their chemical contaminant status (magnitude and extent). Without a status assessment, it is impossible to measure change in a system. This study presents surficial sediment data from Coral and Fish Bays (St. John, US Virgin Islands (USVI)). Portions of these bays are included in Virgin Islands National Park, and Virgin Islands Coral Reef National Monument. A suite of analytes (PCBs, PAHs, pesticides, heavy metals, butyltins) was quantified and compared against other regional data and against previously published sediment quality guidelines (SQG). Contamination from toxic contaminants in the system was generally low when compared to other similar studies and potential toxicity thresholds (SQG). Exceptions to this were copper and total chlordane which exceeded the Effects Range Low (ERL) sediment quality guideline, indicating possible sediment toxicity. This assessment will be useful to coastal managers for tracking environmental change, and ensuring that this marine protected area remains relatively free from toxic contamination.

Metolachlor metabolite (MESA) reveals agricultural nitrate-N fate and transport in Choptank River watershed.

Over 50% of streams in the Chesapeake Bay watershed have been rated as poor or very poor based on the index of biological integrity. The Choptank River estuary, a Bay tributary on the eastern shore, is one such waterway, where corn and soybean production in upland areas of the watershed contribute significant loads of nutrients and sediment to streams. We adopted a novel approach utilizing the relationship between the concentration of nitrate-N and the stable, water-soluble herbicide degradation product MESA {2-[2-ethyl-N-(1-methoxypropan-2-yl)-6-methylanilino]-2-oxoethanesulfonic acid} to distinguish between dilution and denitrification effects on the stream concentration of nitrate-N in agricultural subwatersheds. The ratio of mean nitrate-N concentration/(mean MESA concentration * 1000) for 15 subwatersheds was examined as a function of percent cropland on hydric soil. This inverse relationship (R(2)=0.65, p<0.001) takes into consideration not only dilution and denitrification of nitrate-N, but also the stream sampling bias of the croplands caused by extensive drainage ditch networks. MESA was also used to track nitrate-N concentrations within the estuary of the Choptank River. The relationship between nitrate-N and MESA concentrations in samples collected over three years was linear (0.95 ≤ R(2) ≤ 0.99) for all eight sampling dates except one where R(2)=0.90. This very strong correlation indicates that nitrate-N was conserved in much of the Choptank River estuary, that dilution alone is responsible for the changes in nitrate-N and MESA concentrations, and more importantly nitrate-N loads are not reduced in the estuary prior to entering the Chesapeake Bay. Thus, a critical need exists to minimize nutrient export from agricultural production fields and to identify specific conservation practices to address the hydrologic conditions within each subwatershed. In well drained areas, removal of residual N within the cropland is most critical, and practices such as cover crops which sequester the residual N should be strongly encouraged. In poorly drained areas where denitrification can occur, wetland restoration and controlled drained structures that minimize ditch flow should be used to maximize denitrification.

Organic and metal contamination in marine surface sediments of Guánica Bay, Puerto Rico.

Land based sources of pollution have the potential to adversely impact valuable coral reef ecosystems. In Guánica Bay (Puerto Rico) sediment samples collected and analyzed in 2009 demonstrate unusually high concentrations of total chlordane, total PCBs, nickel and chromium. A variety of other contaminants (total DDT, total PAHs, As, Cu, Hg, and Zn) were also at levels which may indicate sediment toxicity. With the exception of chromium, all of these contaminants were detected in coral tissues (Porites astreoides), although it is unclear at what level these contaminants affect coral health. PCBs and chlordane are environmentally persistent and likely represent legacy pollution from historical uses in close geographic proximity to the Bay. We hypothesize that the high nickel and chromium levels are due to a combination of naturally high Ni and Cr in rock and soils in the watershed, and enhanced (human driven) erosional rates.

Atrazine fate and transport within the coastal zone in southeastern Puerto Rico.

Agrichemical transport to coastal waters may have adverse ecological impact. This work examined atrazine fate and transport in a field adjacent to Puerto Rico's Jobos Bay National Estuarine Research Reserve. The herbicide's use was linked to residue detection in shallow groundwater and movement toward the estuary; however, data indicated that transport via this pathway was small. In contrast, surface runoff as tropical storm systems moved through the area appeared to have high potential for atrazine transport. In this case, transport to the estuary was limited by runoff event timing relative to atrazine application and very rapid atrazine dissipation (DT(50)=1-3 days) in field soil. Soil incubation studies showed that accelerated degradation conditions had developed in the field due to repeated atrazine treatment. To improve weed management, atrazine replacement with other herbicide(s) is recommended. Use of products that have greater soil persistence may increase runoff risk.

Characterization of land-based sources of pollution in Jobos Bay, Puerto Rico: status of heavy metal concentration in bed sediment.

As part of an assessment of land-based sources of pollution in Jobos Bay, Puerto Rico, sediment samples were collected at 43 sites to characterize concentrations of a suite of pollutants, including metals. Fifteen major and trace metals (Ag, Al, As, Cd, Cr, Cu, Fe, Hg, Mn Ni, Pb, Sb, Se, Sn, and Zn) were measured along with total organic carbon and grain size in surficial sediments. For most metals, maximum concentrations were seen in the eastern bay; however, values were still within concentration ranges found in other estuarine systems. In contrast, silver was higher in the western region. In general, metal distribution in the bay was positively correlated with grain size. Additionally, correlations between Al and other metals suggest natural sources for metals. The data presented here suggest that, although the Jobos Bay watershed contains both urban centers along with industrial and agricultural developments, anthropogenic inputs of metals may be negligible.

Characterization of organic chemical contaminants in sediments from Jobos Bay, Puerto Rico.

Jobos Bay, located on the southeastern coast of Puerto Rico, contains a variety of habitats including mangroves, seagrass meadows, and coral reefs. The watershed surrounding the bay includes a number of towns, agricultural areas, and the Jobos Bay National Estuarine Research Reserve (NERR). Jobos Bay and the surrounding watershed are part of a Conservation Effects Assessment Project (CEAP), involving the Jobos Bay NERR, the US Department of Agriculture, and the National Oceanic and Atmospheric Administration (NOAA) to assess the benefits of agricultural best management practices (BMPs) on the terrestrial and marine environments. As part of the Jobos Bay CEAP, NOAA collected sediment samples in May 2008 to characterize over 130 organic chemical contaminants. This paper presents the results of the organic contaminant analysis. The organic contaminants detected in the sediments included polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls, and the pesticide DDT. PAHs at one site in the inner bay near a boat yard were significantly elevated; however, all organic contaminant classes measured were below NOAA sediment quality guidelines that would have indicated that impacts were likely. The results of this work provide an important baseline assessment of the marine environment that will assist in understanding the benefits of implementing BMPs on water quality in Jobos Bay.

Relating nutrient and herbicide fate with landscape features and characteristics of 15 subwatersheds in the Choptank River watershed.

Excess nutrients and agrochemicals from non-point sources contribute to water quality impairment in the Chesapeake Bay watershed and their loading rates are related to land use, agricultural practices, hydrology, and pollutant fate and transport processes. In this study, monthly baseflow stream samples from 15 agricultural subwatersheds of the Choptank River in Maryland USA (2005 to 2007) were characterized for nutrients, herbicides, and herbicide transformation products. High-resolution digital maps of land use and forested wetlands were derived from remote sensing imagery. Examination of landscape metrics and water quality data, partitioned according to hydrogeomorphic class, provided insight into the fate, delivery, and transport mechanisms associated with agricultural pollutants. Mean Nitrate-N concentrations (4.9 mg/L) were correlated positively with percent agriculture (R(2)=0.56) and negatively with percent forest (R(2)=0.60). Concentrations were greater (p=0.0001) in the well-drained upland (WDU) hydrogeomorphic region than in poorly drained upland (PDU), reflecting increased denitrification and reduced agricultural land use intensity in the PDU landscape due to the prevalence of hydric soils. Atrazine and metolachlor concentrations (mean 0.29 µg/L and 0.19 µg/L) were also greater (p=0.0001) in WDU subwatersheds than in PDU subwatersheds. Springtime herbicide concentrations exhibited a strong, positive correlation (R(2)=0.90) with percent forest in the WDU subwatersheds but not in the PDU subwatersheds. In addition, forested riparian stream buffers in the WDU were more prevalent than in the PDU where forested patches are typically not located near streams, suggesting an alternative delivery mechanism whereby volatilized herbicides are captured by the riparian forest canopy and subsequently washed off during rainfall. Orthophosphate, CIAT (6-chloro-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine), CEAT (6-chloro-N-ethyl-1,3,5-triazine-2,4-diamine), and MESA (2-[(2-ethyl-6-methylphenyl) (2-methoxy-1-methylethyl)amino]-2-oxoethanesulfonic acid) were also analyzed. These findings will assist efforts in targeting implementation of conservation practices to the most environmentally-critical areas within watersheds to achieve water quality improvements in a cost-effective manner.

Pollutant fate and spatio-temporal variability in the choptank river estuary: factors influencing water quality.

Restoration of the Chesapeake Bay, the largest estuary in the United States, is a national priority. Documentation of progress of this restoration effort is needed. A study was conducted to examine water quality in the Choptank River estuary, a tributary of the Chesapeake Bay that since 1998 has been classified as impaired waters under the Federal Clean Water Act. Multiple water quality parameters (salinity, temperature, dissolved oxygen, chlorophyll a) and analyte concentrations (nutrients, herbicide and herbicide degradation products, arsenic, and copper) were measured at seven sampling stations in the Choptank River estuary. Samples were collected under base flow conditions in the basin on thirteen dates between March 2005 and April 2008. As commonly observed, results indicate that agriculture is a primary source of nitrate in the estuary and that both agriculture and wastewater treatment plants are important sources of phosphorus. Concentrations of copper in the lower estuary consistently exceeded both chronic and acute water quality criteria, possibly due to use of copper in antifouling boat paint. Concentrations of copper in the upstream watersheds were low, indicating that agriculture is not a significant source of copper loading to the estuary. Concentrations of herbicides (atrazine, simazine, and metolachlor) peaked during early-summer, indicating a rapid surface-transport delivery pathway from agricultural areas, while their degradation products (CIAT, CEAT, MESA, and MOA) appeared to be delivered via groundwater transport. Some in-river processing of CEAT occurred, whereas MESA was conservative. Observed concentrations of herbicide residues did not approach established levels of concern for aquatic organisms. Results of this study highlight the importance of continued implementation of best management practices to improve water quality in the estuary. This work provides a baseline against which to compare future changes in water quality and may be used to design future monitoring programs needed to assess restoration strategy efficacy.

Assessment of eutrophication in estuaries: pressure-state-response and nitrogen source apportionment.

A eutrophication assessment method was developed as part of the National Estuarine Eutrophication Assessment (NEEA) Program. The program is designed to improve monitoring and assessment of eutrophication in the estuaries and coastal bays of the United States with the intent to guide management plans and develop analytical and research models and tools for managers. These tools will help guide and improve management success for estuaries and coastal resources. The assessment method, a Pressure-State-Response approach, uses a simple model to determine Pressure and statistical criteria for indicator variables (where applicable) to determine State. The Response determination is mostly heuristic, although research models are being developed to improve that component. The three components are determined individually and then combined into a single rating. Application to several systems in the European Union (E.U.), specifically in Portugal, shows that the method is transferable, and thus is useful for development of management measures in both the Unites States and E.U. This approach identifies and quantifies the key anthropogenic nutrient input sources to estuaries so that management measures can target inputs for maximum effect. Because nitrogen is often the limiting nutrient in estuarine systems, examples of source identification and quantification for nitrogen have been developed for 11 coastal watersheds on the U.S. east coast using the WATERSN model. In general, estuaries in the Northeastern United States receive most of their nitrogen from human sewage, followed by atmospheric deposition. This is in contrast to some watersheds in the Mid-Atlantic (Chesapeake Bay) and South Atlantic (Pamlico Sound), which receive most of their nitrogen from agricultural runoff. Source identification is important for implementing effective management measures that should be monitored for success using assessment methods, as described herein. For instance, these results suggest that Northeastern estuaries would likely benefit most from improved sewage treatment, where as the Mid and South Atlantic systems would benefit most from agricultural runoff reductions.

Linking hypoxia to shrimp catch in the northern Gulf of Mexico.

Wide spread and reoccurring hypoxia has been observed in the northern Gulf of Mexico since routine monitoring began in the 1980s. Although the potential ecological effects of hypoxia (habitat loss, mortalities) are well known, there is relatively little information linking hypoxia in the northern Gulf of Mexico to fisheries decline. Previous analyses have shown a negative relationship between hypoxic area and brown shrimp (Farfantepenaeus aztecus) catch for the Texas and Louisiana coasts combined from 1985 to 1997. Extending these analyses with data through 2004, we found that the correlation between hypoxic area and landings holds (r=-0.52), plus there was a significant negative relationship (r=-0.59) between hypoxia and shrimp landings for the Texas coast alone. We hypothesize that this pattern is not seen in the Louisiana fishery alone because of differences in fisheries practices (inshore vs. offshore) between Louisiana and Texas.

Importance of atmospherically deposited nitrogen to the annual nitrogen budget of the Neuse River estuary, North Carolina.

Wet deposition of nitrogen, as NH(4)(+), NO(3)(-), and organic N, contributes up to 50% of the total externally supplied or 'new' N flux to the Neuse River Estuary (North Carolina). Excessive nitrogen (N) loading to N-sensitive waters such as the Neuse River Estuary has been linked to changes in microbial and algal community composition and function (harmful algal blooms), hypoxia/anoxia, and fish kills. In a 4-year study from July 1996 to July 2000, the weekly wet deposition of NH(4)(+), NO(3)(-), and dissolved organic N was calculated, based on concentration and precipitation measurements, at 11 sites on a northwest-southeast transect in the watershed. Data from this period indicate that the annual mean total wet atmospherically deposited (AD)-N flux was 11 kg ha(-1) year(-1). Deposition was fairly evenly distributed between nitrate, ammonium, and organics (32%, 32%, and 36%, respectively). Seasonally, the summer (June-August) months contained the highest weekly wet total N deposition; this trend was not driven by precipitation amount. Estimates of watershed N retention and in-stream riverine processing revealed that the AD-N flux contributed an estimated 20% (range of 15-51%) of the total 'new' N flux to the estuary, with direct deposition of N to the estuary surface accounting for 6% of the total 'new' N flux. This study did not measure the dry depositional flux, which may double the contribution of AD-N to the estuary. The AD-N is an important source of 'new' N to the Neuse River Estuary as well as other estuarine and coastal ecosystems downwind of major emission sources. As such, AD-N should be included in effective nutrient mitigation and management efforts for these N-sensitive waters.