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.

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.

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.