Phosphorus retention and remobilization in vegetated buffer strips: a review

Diffuse pollution remains a major threat to surface waters due to eutrophication caused by phosphorus (P) transfer from agricultural land. Vegetated buffer strips (VBSs) are increasingly used to mitigate diffuse P losses from agricultural land, having been shown to reduce particulate P transfer. However, retention of dissolved P (DP) has been lower, and in some cases VBSs have increased delivery to surface waters. The aims of this review were (i) to develop a conceptual model to enhance the understanding of VBS functioning in terms of DP, (ii) to identify key processes within the model that affect DP retention and delivery, and (iii) to explore evidence for the controls on these processes. A greater understanding in these areas will allow the development of management strategies that enhance DP retention. We found evidence of a surface layer in buffer strip soils that is enriched in soluble P compared with adjacent agricultural land and may be responsible for the reported increased DP delivery. Through increased biological activity in VBSs, plants and microorganisms may assimilate P from particulates retained in the VBSs or native soil P and remobilize this P in a more soluble form. These conclusions are based on a limited amount of research, and a better understanding of biogeochemical cycling of P in buffer strip soils is required.     

A coastal cliff management district for protection of eroding high relief coasts

Ensuring that new buildings do not interfere with the recreational and protective functions of the natural system and that the buildings will be useful long enough to protect the investment are among long-term solutions to coastal erosion. We propose that coastal cliff management districts be established for management of eroding high relief shorelines. Such districts would include an imminent failure zone, in which bluff retreat is possible at any time; a migration zone, which allows for long-term shoreline retreat; and a stability control zone in which activities affecting bluff erosion are restricted. Procedures are described for delineating these zones based on geomorphic criteria. If these land use controls are implemented, some shorefront development can be accommodated while retaining valuable characteristics of the natural system.     

Volatilization and degradation of soil-applied dimethylselenide

Dimethylselenide (DMSe) is a highly volatile gas that is produced by indigenous microorganisms in seleniferous soils and sediments; however, little is known about the soil conditions that affect the persistence of DMSe and its transport to the atmosphere. In this study we investigated the effect of moisture content, temperature, and organic amendments on the degradation of soil-applied DMSe. The degradation of DMSe was entirely a result of biological mechanisms, but changes in temperature (20-40 degrees C) and soil moisture content (30-70% of the maximum water holding capacity) had little influence on the degradation rate. In contrast, amending soil with either 1% casein or gluten (by weight) had an inhibitory effect on the degradation of DMSe. After 18 d, 2.1 times more DMSe was present in the casein-amended soil and 2.6 times more DMSe was present in the gluten-amended soil. The transport of DMSe in packed soil columns was also investigated. Increasing the depth to soil surface was found to significantly decrease the amount of DMSe transported to the air. After 6 d, 57% of DMSe injected 10 cm below the soil surface was volatilized. At an injection depth of 20 cm the cumulative emissions were reduced by 38% and at 30 cm the cumulative emissions were reduced by 51%. In columns containing 1% casein or gluten in the top 5 cm of soil the cumulative loss of DMSe was about 9% higher than in unamended soil. Increasing our understanding of the soil conditions that influence the gaseous diffusion of DMSe should help in determining the feasibility of using Se volatilization as a remediation technique.     

Nitrogen deposition effects on Mediterranean-type ecosystems: an ecological assessment

We review the ecological consequences of N deposition on the five Mediterranean regions of the world. Seasonality of precipitation and fires regulate the N cycle in these water-limited ecosystems, where dry N deposition dominates. Nitrogen accumulation in soils and on plant surfaces results in peaks of availability with the first winter rains. Decoupling between N flushes and plant demand promotes losses via leaching and gas emissions. Differences in P availability may control the response to N inputs and susceptibility to exotic plant invasion. Invasive grasses accumulate as fuel during the dry season, altering fire regimes. California and the Mediterranean Basin are the most threatened by N deposition; however, there is limited evidence for N deposition impacts outside of California. Consequently, more research is needed to determine critical loads for each region and vegetation type based on the most sensitive elements, such as changes in lichen species composition and N cycling.     

Environmental photodegradation of mefenamic acid

Pharmaceuticals and personal care products are an emerging class of environmental pollutants. Photolysis is expected to be a major loss process for many of these compounds in surface waters, including the common non-steroidal anti-inflammatory drug mefenamic acid. The direct photolysis solar quantum yield of mefenamic acid was observed to be 1.5+/-0.3x10(-4). Significant photosensitization was observed in solutions of Suwanee River fulvic acid and Mississippi River water, as well as for the model photosensitization compounds 3'-methoxyacetophenone, 2-acetonaphthone and perinaphthenone. Quenching, sparging and light-filtering experiments suggested a direct reaction of mefenamic acid with excited triplet-state dissolved organic matter as the major photosensitization process. The persistence of the model photosensitizer suggests that the photosensitization by perinaphthenone occurs either by triplet-energy transfer or an electron transfer followed by rapid regeneration of the sensitizer. Due to its low quantum yield, the loss of mefenamic acid in sunlit natural waters is expected to depend on both direct and indirect photodegradation processes.     

Deriving fuel-based emission factor thresholds to interpret heavy-duty vehicle roadside plume measurements

Remote sensing devices have been used for decades to measure gaseous emissions from individual vehicles at the roadside. Systems have also been developed that entrain diluted exhaust and can also measure particulate matter (PM) emissions. In 2015, the California Air Resources Board (CARB) reported that 8% of in-field diesel particulate filters (DPF) on heavy-duty (HD) vehicles were malfunctioning and emitted about 70% of total diesel PM emissions from the DPF-equipped fleet. A new high-emitter problem in the heavy-duty vehicle fleet had emerged. Roadside exhaust plume measurements reflect a snapshot of real-world operation, typically lasting several seconds. In order to relate roadside plume measurements to laboratory emission tests, we analyzed carbon dioxide (CO₂), oxides of nitrogen (NO_X), and PM emissions collected from four HD vehicles during several driving cycles on a chassis dynamometer. We examined the fuel-based emission factors corresponding to possible exceedances of emission standards as a function of vehicle power. Our analysis suggests that a typical HD vehicle will exceed the model year (MY) 2010 emission standards (of 0.2 g NO_X/bhp-hr and 0.01 g PM/bhp-hr) by three times when fuel-based emission factors are 9.3 g NO_X/kg fuel and 0.11 g PM/kg using the roadside plume measurement approach. Reported limits correspond to 99% confidence levels, which were calculated using the detection uncertainty of emissions analyzers, accuracy of vehicle power calculations, and actual emissions variability of fixed operational parameters. The PM threshold was determined for acceleration events between 0.47 and 1.4 mph/sec only, and the NO_X threshold was derived from measurements where after-treatment temperature was above 200°C. Anticipating a growing interest in real-world driving emissions, widespread implementation of roadside exhaust plume measurements as a compliment to in-use vehicle programs may benefit from expanding this analysis to a larger sample of in-use HD vehicles.

Implications: Regulatory agencies, civil society, and the public at large have a growing interest in vehicle emission compliance in the real world. Leveraging roadside plume measurements to identify vehicles with malfunctioning emission control systems is emerging as a viable new and useful method to assess in-use performance. This work proposes fuel-based emission factor thresholds for PM and NOx that signify exceedances of emission standards on a work-specific basis by analyzing real-time emissions in the laboratory. These thresholds could be used to prescreen vehicles before roadside enforcement inspection or other inquiry, enhance and further develop emission inventories, and potentially develop new requirements for heavy-duty inspection and maintenance (I/M) programs, including but not limited to identifying vehicles for further testing.     

Source contributions to the mutagenicity of urban particulate air pollution

Using organic compounds as tracers, a chemical mass balance model was employed to investigate the relationship between the mutagenicity of the urban organic aerosol sources and the mutagenicity of the atmospheric samples. The fine particle organic mass concentration present in the 1993 annual average Los Angeles-area composite sample was apportioned among eight emission source types. The largest source contributions to fine particulate organic compound mass concentration were identified as smoke from meat cooking, diesel-powered vehicle exhaust, wood smoke, and paved road dust. However, the largest source contributions to the mutagenicity of the atmospheric sample were natural gas combustion and diesel-powered vehicles. In both the human cell and bacterial assay systems, the combined mutagenicity of the composite of primary source effluents predicted to be present in the atmosphere was statistically indistinguishable from the mutagenicity of the actual atmospheric sample composite. Known primary emissions sources appear to be capable of emitting mutagenic organic matter to the urban atmosphere in amounts sufficient to account for the observed mutagenicity of the ambient samples. The error bounds on this analysis, however, are wide enough to admit to the possible importance of additional mutagenic organics that are formed by atmospheric reaction (e.g., 2-nitrofluoranthene has been identified as an important human cell mutagen in the atmospheric composite studied here, accounting for approximately 1% of the total sample mutagenic potency).     

Experimental variability in characterization of cyfluthrin sorption to soil

To assess the risk of a pesticide to leach to groundwater or to run off to surface water after application, it is necessary to characterize the sorption of the pesticide to soil. For pyrethroids, their hydrophobicity, strong sorption to various materials, and low solubility make it difficult to accurately characterize sorption processes. The objective of this research was to evaluate the variability in cyfluthrin ((RS)-alpha -cyano-4-fluoro-3-phenoxybenzyl (1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate) sorption to soil as affected by experiment conditions. To minimize cyfluthrin sorption on the walls of glass, silanized-glass, stainless steel, and PTFE centrifuge tubes, cyfluthrin solution was added to aqueous soil slurries or directly to soil, after which it was equilibrated with aqueous solution. Depending on the soil, variation in sorption coefficients, Koc, obtained using different experimental methodologies with one soil can be comparable to the variation in Koc values obtained for soils with different physical and chemical properties using one method. Koc values for cyfluthrin ranged from 56,000 to 300,000 L kg-1. Sorption methodology needs to be evaluated before sorption coefficients are used in predictive transport models.