Investigation of the Ultraviolet Photolysis Method for the Determination of Organic Nitrogen in Aerosol Samples

Abstract

The research objective was to adapt the ultraviolet (UV)photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2² factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 °C occurred at pH 2.0 with a 24-hr irradiance period at concentrations < µM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH₄ ⁺), but urea released a near equimolar ratio of NH₄ ⁺ and nitrate (NO₃ ^?). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM₁₀ were 78.1 ± 29.2 nmol-Nm^?3and 8.3 ± 4.9 nmol-Nm^?3, respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 ± 5.7%, and the majority of the DON (79.1 ± 18.2%) was found in the fine particulate matter (PM_2.5) fraction. The average concentrations of DIN and DON in the PM_2.5 fraction were 54.4 ± 25.6 nmol-Nm^?3 and 6.5 ± 4.4 nmol-Nm^?3, respectively.     

Responses of Hyalella azteca and phytoplankton to a simulated agricultural runoff event in a managed backwater wetland

We assessed the aqueous toxicity mitigation capacity of a hydrologically managed floodplain wetland following a synthetic runoff event amended with a mixture of sediments, nutrients (nitrogen and phosphorus), and pesticides (atrazine, S-metolachlor, and permethrin) using 48-h Hyalella azteca survival and phytoplankton pigment, chlorophyll a. The runoff event simulated a 1 h, 1.27 cm rainfall event from a 16 ha agricultural field. Water (1 L) was collected every 30 min within the first 4 h, every 4 h until 48 h, and on days 5, 7, 14, 21, and 28 post-amendment at distances of 0, 10, 40, 300 and 500 m from the amendment point for chlorophyll a, suspended sediment, nutrient, and pesticide analyses. H. azteca 48-h laboratory survival was assessed in water collected at each site at 0, 4, 24, 48 h, 5 d and 7 d. Greatest sediment, nutrient, and pesticide concentrations occurred within 3 h of amendment at 0 m, 10 m, 40 m, and 300 m downstream. Sediments and nutrients showed little variation at 500 m whereas pesticides peaked within 48 h but at <15% of upstream peak concentrations. After 28 d, all mixture components were near or below pre-amendment concentrations. H. azteca survival significantly decreased within 48 h of amendment up to 300 m in association with permethrin concentrations. Chlorophyll a decreased within the first 24 h of amendment up to 40 m primarily in conjunction with herbicide concentrations. Variations in chlorophyll a at 300 and 500 m were associated with nutrients. Managed floodplain wetlands can rapidly and effectively trap and process agricultural runoff during moderate rainfall events, mitigating impacts to aquatic invertebrates and algae in receiving aquatic systems.     

Cost‐Effective Sediment Dredge Disposal Options for Small Craft Harbors in Canada

Sediment dredge disposal options were reviewed to improve cost‐effectiveness and environmental safety for dredging of coastal sediments at the Department of Fisheries and Oceans Small Craft Harbours (DFO‐SCH) program in Canada. Historically, contaminated dredge sediments exceeding federal guidelines were disposed of in nearby landfills. Recent federal regulatory changes in sediment quality guidelines adopted by provincial regulators in Canada has resulted in updates to guidelines for disposal of contaminated solids in landfills. Updates now require specific and general disposal options for contaminated dredge material destined for land‐based disposal, resulting in more expensive disposal in containment cells (if contaminated sediments exceed federal guidelines). However, as part of this study, a leachate testing method was applied to contaminated sediments to simulate migration of potential contaminants in groundwater. Using this approach, leachate quality was compared to federal freshwater criteria and drinking water quality guidelines for compliance with new regulations. Leachate testing performed on the highest sediment contaminant concentrations triggered less than 2 percent potable water exceedances, meaning that most dredge spoils could be disposed of in privately owned or provincially operated landfill sites, providing less expensive disposal options compared to containment cell disposal. Current dredge disposal practices were reviewed at 35 harbor sites across Nova Scotia and their limitations identified in a gap analysis. Improved site management was developed following this review and consultation with interested marine stakeholders. New disposal options and chemical analyses were proposed, along with improvements to cost efficiencies for management of dredged marine sediments in Atlantic Canada. © 2013 Wiley Periodicals, Inc.     

The effect of certain intrinsic and extrinsic variables on the acute toxicity of selected organophosphorus insecticides to the mummichog,Fundulus heteroclitus

Abstract

The acute toxicity of two organophosphorus (OP) insecticides, azinphosmethyl and acephate, was evaluated in the mummichog, Fundulus heteroclitus. In addition, the effects of certain intrinsic (sex) and extrinsic (salinity and multiple toxicant interraction) variables on the toxic response were also investigated. Azinphosmethyl was by far the most toxic of the two OP insecticides with a 96h LC50 ～ 100,000 x lower than that for acephate. Slight sex differences were observed in the sensitivity of mummichogs to each of the OP insecticides with male fish being marginally more sensitive. Significant effects of low salinity stress were observed only with acephate exposure and, in this case, low salinity appeared to be slightly protective. In general, all of the insecticide mixtures (azinphosmethyl/endosulfan, azinphosmethyl/fenvalerate and acephate/fenvalerate) tested exhibited simple additive toxicity.     

The chronic toxicity of fenoxycarb to larvae of the grass shrimp,Palaemonetes pugio

Abstract

This study examined effects of fenoxycarb, a carbamate insecticide, on larvae of the grass shrimp, Palaemonetes pugio. In laboratory experiments, grass shrimp larvae were exposed to fenoxycarb from hatch to postlarval metamorphosis in a chronic, static renewal bio assay. LC50's ranged from 0.92 mg/L at 96 h to 0.35 mg/L at the end of the study (24 days). In assessing sublethal effects of fenoxycarb, postlarval emergence was significantly (p < 0.05) reduced in exposed grass shrimp as compared with controls, and the time to reach postlarval status was significantly (p < 0.05) increased in exposed grass shrimp. Significant differences were not found in other sublethal parameters including postlarval dry weight and intermolt duration. Analysis of fenoxycarb from spiked seawater samples showed concentrations declined by 32 to 42% after 24 h.     

Investigation of an Escherichia coli environmental benchmark for waterborne pathogens in agricultural watersheds in Canada

Canada's National Agri-Environmental Standards Initiative sought to develop an environmental benchmark for low-level waterborne pathogen occurrence in agricultural watersheds. A field study collected 902 water samples from 27 sites in four intensive agricultural watersheds across Canada from 2005 to 2007. Four of the sites were selected as reference sites away from livestock and human fecal pollution sources in each watershed. Water samples were analyzed for Campylobacter spp., Salmonella spp., Escherichia coli O157:H7, Cryptosporidium spp., Giardia spp., and the water quality indicator E. coli. The annual mean number of pathogen species was higher at agricultural sites (1.54 ± 0.07 species per water sample) than at reference sites (0.75 ± 0.14 species per water sample). The annual mean concentration of E. coli was also higher at agricultural sites (491 ± 96 colony-forming units [cfu] 100 mL(-1)) than at reference sites (53 ± 18 cfu 100 mL(-1)). The feasibility of adopting existing E. coli water quality guideline values as an environmental benchmark was assessed, but waterborne pathogens were detected at agricultural sites in 80% of water samples with low E. coli concentrations (<100 cfu 100 mL(-1)). Instead, an approach was developed based on using the natural background occurrence of pathogens at reference sites in agricultural watersheds to derive provisional environmental benchmarks for pathogens at agricultural sites. The environmental benchmarks that were derived were found to represent E. coli values lower than geometric mean values typically found in recreational water quality guidelines. Additional research is needed to investigate environmental benchmarks for waterborne pathogens within the context of the "One World, One Health" perspective for protecting human, domestic animal, and wildlife health.     

Optimal control of soybean aphid in the presence of natural enemies and the implied value of their ecosystem services

By suppressing pest populations, natural enemies provide an important ecosystem service that maintains the stability of agricultural ecosystems systems and potentially mitigates producers' pest control costs. Integrating natural control services into decisions about pesticide-based control has the potential to significantly improve the economic efficiency of pesticide use, with socially desirable outcomes. Two gaps have hindered the incorporation of natural enemies into pest management decision rules: (1) insufficient knowledge of pest and predator population dynamics and (2) lack of a decision framework for the economic tradeoffs among pest control options. Using a new intra-seasonal, dynamic bioeconomic optimization model, this study assesses how predation by natural enemies contributes to profit-maximizing pest management strategies. The model is applied to the management of the invasive soybean aphid, the most significant serious insect threat to soybean production in North America. The resulting lower bound estimate of the value of natural pest control ecosystem services was estimated at $84 million for the states of Illinois, Indiana, Iowa, Michigan and Minnesota in 2005.     

A Framework for Responding to Coral Disease Outbreaks that Facilitates Adaptive Management

Predicted increases in coral disease outbreaks associated with climate change have implications for coral reef ecosystems and the people and industries that depend on them. It is critical that coral reef managers understand these implications and have the ability to assess and reduce risk, detect and contain outbreaks, and monitor and minimise impacts. Here, we present a coral disease response framework that has four core components: (1) an early warning system, (2) a tiered impact assessment program, (3) scaled management actions and (4) a communication plan. The early warning system combines predictive tools that monitor the risk of outbreaks of temperature-dependent coral diseases with in situ observations provided by a network of observers who regularly report on coral health and reef state. Verified reports of an increase in disease prevalence trigger a tiered response of more detailed impact assessment, targeted research and/or management actions. The response is scaled to the risk posed by the outbreak, which is a function of the severity and spatial extent of the impacts. We review potential management actions to mitigate coral disease impacts and facilitate recovery, considering emerging strategies unique to coral disease and more established strategies to support reef resilience. We also describe approaches to communicating about coral disease outbreaks that will address common misperceptions and raise awareness of the coral disease threat. By adopting this framework, managers and researchers can establish a community of practice and can develop response plans for the management of coral disease outbreaks based on local needs. The collaborations between managers and researchers we suggest will enable adaptive management of disease impacts following evaluating the cost-effectiveness of emerging response actions and incrementally improving our understanding of outbreak causation.     

Locating Spatial Variation in the Association Between Wildland Fire Risk and Social Vulnerability Across Six Southern States

Wildland fire in the South commands considerable attention, given the expanding wildland urban interface (WUI) across the region. Much of this growth is propelled by higher income retirees and others desiring natural amenity residential settings. However, population growth in the WUI increases the likelihood of wildfire fire ignition caused by people, as humans account for 93% of all wildfires fires in the South. Coexisting with newly arrived, affluent WUI populations are working class, poor or otherwise socially vulnerable populations. The latter groups typically experience greater losses from environmental disasters such as wildfire because lower income residents are less likely to have established mitigation programs in place to help absorb loss. We use geographically weighted regression to examine spatial variation in the association between social vulnerability (SOVUL) and wildfire risk. In doing so, we identify “hot spots” or geographical clusters where SOVUL varies positively with wildfire risk across six Southern states—Alabama, Arkansas, Florida, Georgia, Mississippi, and South Carolina. These clusters may or may not be located in the WUI. These hot spots are most prevalent in South Carolina and Florida. Identification of these population clusters can aid wildfire managers in deciding which communities to prioritize for mitigation programming.     

Water quality effects of clearcut harvesting and forest fertilization with best management practices

Nine small (2.5 ha) and four large (70-135 ha) watersheds were instrumented in 1999 to evaluate the effects of silvicultural practices with application of best management practices (BMPs) on stream water quality in East Texas, USA. Two management regimes were implemented in 2002: (i) conventional, with clearcutting, herbicide site preparation, and BMPs and (ii) intensive, which added subsoiling, aerial broadcast fertilization, and an additional herbicide application. Watershed effects were compared with results from a study on the same small watersheds in 1981, in which two combinations of harvesting and mechanical site preparation without BMPs or fertilization were evaluated. Clearcutting with conventional site preparation resulted in increased nitrogen losses on the small watersheds by about 1 additional kg ha(-1) each of total Kjeldahl nitrogen (TKN) and nitrate-nitrogen (NO(3)-N) in 2003. First-year losses were not significantly increased on the large watershed with a conventional site preparation with BMPs. Fertilization resulted in increased runoff losses in 2003 on the intensive small watersheds by an additional 0.77, 2.33, and 0.36 kg ha(-1) for NO(3)-N, TKN, and total phosphorus, respectively. Total loss rates of ammonia nitrogen (NH(4)-N) and NO(3)-N were low overall and accounted for only approximately 7% of the applied N. Mean loss rates from treated watersheds were much lower than rainfall inputs of about 5 kg ha(-1) TKN and NO(3)-N in 2003. Aerial fertilization of the 5-yr-old stand on another large watershed did not increase nutrient losses. Intensive silvicultural practices with BMPs did not significantly impair surface water quality with N and P.