Detection and accumulation of environmentally-relevant glyphosate concentrations delivered via pulse- or continuous-delivery on passive samplers.

Glyphosate is the most commonly used herbicide globally, which has contributed to its ubiquitous presence in the environment. Glyphosate application rates and delivery to surface water vary with land use. Streams in urban and agricultural catchments can experience continuous delivery of low concentrations of glyphosate and aminomethylphosphonic acid (AMPA), while their presence in forest streams occurs as an episodic pulse following silvicultural application. We assessed whether trace concentrations of glyphosate delivered as a 1-day pulse (mimic silvicultural applications) followed by flushing with deionized water would affect the detection of glyphosate or AMPA on novel passive samplers, Polar Organic Chemical Integrative Sampler with Molecular Imprinted Polymer (POCIS-MIP), compared with continuous delivery (mimic agricultural or urban applications). Within each delivery type, POCIS-MIP were exposed to seven treatment concentrations of Rodeo (equivalent to 0.0 to 1.84 µg glyphosate L-1). Experimental results demonstrate POCIS-MIP can detect differences in relative glyphosate concentrations above 0.115 µg L-1 (pulse-delivery) or 0.23 µg L-1 (continuous-delivery), but were unable to distinguish trace concentrations (i.e., < 0.115 or 0.23 µg L-1). Our results suggest POCIS-MIP may better retain glyphosate when delivered as a pulse than when delivered continuously, but both underestimated actual treatment concentrations by 46 to 56%. There is a need to demonstrate the field applicability of passive sampling methods to improve environmental monitoring of silvicultural herbicides, and our results demonstrate passive samplers were unable to distinguish lower concentrations, suggesting a limited utility for determining trace concentration levels such as those experienced during or immediately after silvicultural application.

A long-term, multitrophic level study to assess pulp and paper mill effluent effects on aquatic communities in four US receiving waters: characteristics of the study streams, sample sites, mills, and mill effluents.

Watershed characteristics, study streams, sample sites, mills, and mill effluents are provided for 4 streams included in a long-term study to assess potential effects of pulp and paper mill effluents on US receiving waters. The study streams are Codorus Creek (Pennsylvania, USA), Leaf River (Mississippi, USA) and McKenzie and Willamette rivers (Oregon, USA) and were chosen to represent a blend of mill process types, effluent concentrations, and coldwater/warmwater stream systems. The described effluent quality, water quality, and habitat data sets encompass the initial 7 to 8 y of a study anticipated to continue >10 y and provide a backdrop to a series of articles describing periphyton, macroinvertebrate, and fish community properties in these same streams. The mean in-stream waste concentration (IWC) for these 4 effluent discharges was 32.4%, 2.0%, 0.5%, and 0.2% v/v for Codorus Creek and Leaf, McKenzie, and Willamette rivers, respectively, as compared with a median of 0.4% for US mills. Effluent quality measurements included Selenastrum capricornutum, Ceriodaphnia dubia, and Pimephales promelas chronic bioassays as sanctioned by the US Environmental Protection Agency for estimating effluent effects on receiving-water aquatic communities. Based on mean bioassay inhibition concentration for a 25% effect and on mean IWC, a margin of safety against adverse biological effects of 2, 25, 137, and 150 times was indicated for Codorus Creek and Leaf, McKenzie, and Willamette rivers, respectively. Habitat and water quality assessment was carried out over a gradient of sample sites above and below the effluent discharge to determine nonmill-related conditions that might interfere with interpretation of effluent effects. Noneffluent related localized differences in conditions for some parameters, including current velocity (McKenzie River), and surface incident photosynthetically active radiation (Codorus Creek and Willamette River) occurred at the sample stations immediately upstream or downstream of the effluent discharge. In addition, broader watershed differences were evident on Codorus Creek, where a relatively rich riparian corridor and stream structure occurred upstream in contrast to areas of canopy and stream-structure loss in the downstream urban area. The mill effluent discharges contributed to increases in receiving-water color and conductivity, although upstream tributaries contributed additional conductivity to Codorus Creek and color to the Leaf River. The McKenzie River provided the only example of a nutrient increase immediately downstream of a mill discharge. This increase in total nitrogen (0.11 vs 0.16 mg/L) could not, however, be differentiated with respect to whether it was of mill effluent or tributary stream origin. Tributary streams were potentially important total nitrogen contributors on Codorus Creek and the Willamette River. As an integrated study, the effluent quality and physical/chemical watershed descriptions provided here represent 1 component of the broader study addressing potential point-source effluent effects within the context of the larger watershed and a multiyear timescale. The absence of effluent-related in-stream chemical/physical responses, other than increases in conductivity and color, and a considerable bioassay-based margin of safety, provides for a working hypothesis that there will be no effluent-related biological population/community responses from these 4 mill discharges. This hypothesis, as it relates to periphyton, macroinvertebrate, and fish communities, will be addressed in other articles in this series.