Source estimation methods for atmospheric dispersion

Both forward and backward transport modeling methods are being developed for characterization of sources in atmospheric releases of toxic agents. Forward modeling methods, which describe the atmospheric transport from sources to receptors, use forward-running transport and dispersion models or computational fluid dynamics models which are run many times, and the resulting dispersion field is compared to observations from multiple sensors. Forward modeling methods include Bayesian updating and inference schemes using stochastic Monte Carlo or Markov Chain Monte Carlo sampling techniques. Backward or inverse modeling methods use only one model run in the reverse direction from the receptors to estimate the upwind sources. Inverse modeling methods include adjoint and tangent linear models, Kalman filters, and variational data assimilation, among others.This survey paper discusses these source estimation methods and lists the key references. The need for assessing uncertainties in the characterization of sources using atmospheric transport and dispersion models is emphasized.     

Impact of Climate Change on Ecological Quality Indicators and Biogeochemical Fluxes in the Baltic Sea: A Multi-Model Ensemble Study

Multi-model ensemble simulations using three coupled physical-biogeochemical models were performed to calculate the combined impact of projected future climate change and plausible nutrient load changes on biogeochemical cycles in the Baltic Sea. Climate projections for 1961-2099 were combined with four nutrient load scenarios ranging from a pessimistic business-as-usual to a more optimistic case following the Helsinki Commission's (HELCOM) Baltic Sea Action Plan (BSAP). The model results suggest that in a future climate, water quality, characterized by ecological quality indicators like winter nutrient, summer bottom oxygen, and annual mean phytoplankton concentrations as well as annual mean Secchi depth (water transparency), will be deteriorated compared to present conditions. In case of nutrient load reductions required by the BSAP, water quality is only slightly improved. Based on the analysis of biogeochemical fluxes, we find that in warmer and more anoxic waters, internal feedbacks could be reinforced. Increased phosphorus fluxes out of the sediments, reduced denitrification efficiency and increased nitrogen fixation may partly counteract nutrient load abatement strategies.     

High Volume Sampling:Evaluation of an Inverted Sampler for Ambient TSP Measurements

Recent advances in the development of receptor-oriented source apportionment techniques (models) have provided a new approach to evaluating the performance of particulate dispersion models. Rather than limiting performance evaluations to comparisons of particulate mass, receptor model estimates of source impacts can be used to open new opportunities for in-depth analysis of dispersion model performance. Recent experiences in the joint application of receptor and dispersion models have proven valuable in developing increased confidence in source impact projections used for control strategy development. Airshed studies that have followed this approach have identified major errors in emission inventory data bases and provided technical support for modeling assumptions.

This paper focuses on the joint application of dispersion and receptor models to particulate source impact analysis and dispersion model performance and evaluation. The limitations and advantages of each form of modeling are reviewed and case studies are examined. The paper is offered to provide several new perspectives into the model evaluation process in the hope that they may prove useful to those that manage our nation’s air resources.     

PM Fine Standards and Implied Modeling/Analysis Needs

ABSTRACT

New National Ambient Air Quality Standards (NAAQS) were promulgated for fine particulate matter (FPM) in July 1997. This paper summarizes likely timing for implementing programs to meet these standards, which have a bearing on future modeling/analysis needs. The paper notes technical requirements implied by the nature of the NAAQS, as well as feedback the agency has received concerning modeling/analysis through Federal Advisory Committee Act (FACA) subcommittee work groups. Conclusions and recommendations drawn from recently completed U.S. Environmental Protection Agency (EPA)- sponsored workshops on modeling and other source attribution techniques are also described. Efforts to respond to needs implied by the NAAQS and feedback are noted by outlining major topics and issues that future guidance on use of modeling and other analyses used for attainment demonstrations will need to address. The paper concludes by highlighting several as yet unmet modeling/analysis needs to support a well-founded strategy for meeting air quality goals for FPM. These are suggested as potential areas for policy-relevant research.     

Evolution of Organic Analytical Methods in Environmental Forensic Chemistry

Over the past few decades the development of environmental regulations, advances in analytical chemistry and other scientific disciplines, and increased rigor in quality control procedures have created a new discipline, environmental forensics. The need for analytical methods that determine qualitatively and quantitatively organic compounds in the environment, especially in drinking waters, was recognized in the early 1950s. These methods were developed gradually by the early 1960s. The important tools of gas chromatography and mass spectroscopy that evolved in the 1970s provided the early environmental forensic chemist for the first time with the ability to produce scientifically sound data that was admissible in court. By the 1990s, multivariate statistical techniques became available and accepted, including principal component analysis (PCA) and polytopic vector analysis (PVA). These techniques, coupled with the advancing analytical methods, have enabled forensic investigator tools to evaluate and demonstrate unique attributes of a set of data. Analyses of marker compounds, PCBs, PCDD/Fs and petroleum hydrocarbons are all shown to be potentially valuable in deciphering the source and fate of contamination. This paper shows how advancements in environmental analytical chemistry provide the forensic chemist with tools to assess the source(s) of site contamination.     

Evolution of Organic Analytical Methods in Environmental Forensic Chemistry

Over the past few decades the development of environmental regulations, advances in analytical chemistry and other scientific disciplines, and increased rigor in quality control procedures have created a new discipline, environmental forensics. The need for analytical methods that determine qualitatively and quantitatively organic compounds in the environment, especially in drinking waters, was recognized in the early 1950s. These methods were developed gradually by the early 1960s. The important tools of gas chromatography and mass spectroscopy that evolved in the 1970s provided the early environmental forensic chemist for the first time with the ability to produce scientifically sound data that was admissible in court. By the 1990s, multivariate statistical techniques became available and accepted, including principal component analysis (PCA) and polytopic vector analysis (PVA). These techniques, coupled with the advancing analytical methods, have enabled forensic investigator tools to evaluate and demonstrate unique attributes of a set of data. Analyses of marker compounds, PCBs, PCDD/Fs and petroleum hydrocarbons are all shown to be potentially valuable in deciphering the source and fate of contamination. This paper shows how advancements in environmental analytical chemistry provide the forensic chemist with tools to assess the source(s) of site contamination.     

Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI FT-ICR MS): Characterization of Complex Environmental Mixtures

Structural and chemical characterization of compounds within complex environmental mixtures provides unique insights into the roles of these compounds in different environmental processes. Here, an emerging technique in environmental chemistry, electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS), is described and its applications to the molecular characterization of humic acids and petroleum products are reviewed and examined. ESI is a low-fragmentation ionization technique that preferentially ionizes polar functional groups prior to mass spectrometric analysis. This technique allows the characterization of intact polar macromolecules that are inaccessible to standard chromatographic techniques. ICR MS is an ultrahigh resolution and mass accuracy MS technique based on the detection of ion cyclotron motion within a magnetic field. The combination of ESI FT-ICR MS with other structural techniques such as nuclear magnetic resonance (NMR) allows the unprecedented identification and characterization of polar macromolecules in environmental mixtures and will find numerous applications within environmental chemistry and forensics.     

Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI FT-ICR MS): Characterization of Complex Environmental Mixtures

Structural and chemical characterization of compounds within complex environmental mixtures provides unique insights into the roles of these compounds in different environmental processes. Here, an emerging technique in environmental chemistry, electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS), is described and its applications to the molecular characterization of humic acids and petroleum products are reviewed and examined. ESI is a low-fragmentation ionization technique that preferentially ionizes polar functional groups prior to mass spectrometric analysis. This technique allows the characterization of intact polar macromolecules that are inaccessible to standard chromatographic techniques. ICR MS is an ultrahigh resolution and mass accuracy MS technique based on the detection of ion cyclotron motion within a magnetic field. The combination of ESI FT-ICR MS with other structural techniques such as nuclear magnetic resonance (NMR) allows the unprecedented identification and characterization of polar macromolecules in environmental mixtures and will find numerous applications within environmental chemistry and forensics.     

Chemical behavior of residential lead in urban yards in the United States

Long after federal regulations banned the use of lead-based paints and leaded gasoline, residential lead remains a persistent challenge. Soil lead is a significant contributor to this hazard and an improved understanding of physicochemical properties is likely to be useful for in situ abatement techniques such as phytoremediation and chemical stabilization. A laboratory characterization of high-lead soils collected from across the United States shows that the lead contaminants were concentrating in the silt and clay fractions, in the form of discrete particles of lead, as observed by scanning electron microscopy coupled with energy dispersive X-ray analysis. Soil lead varied widely in its solubility behavior as assessed by sequential and chelate extractions. Because site-specific factors (e.g., soil pH, texture, etc.) are believed to govern the solubility of the lead, understanding the variability in these characteristics at each site is necessary to optimize in situ remediation or abatement of these soils.     

Measuring atmospheric composition change

Scientific findings from the last decades have clearly highlighted the need for a more comprehensive approach to atmospheric change processes. In fact, observation of atmospheric composition variables has been an important activity of atmospheric research that has developed instrumental tools (advanced analytical techniques) and platforms (instrumented passenger aircrafts, ground-based in situ and remote sensing stations, earth observation satellite instruments) providing essential information on the composition of the atmosphere. The variability of the atmospheric system and the extreme complexity of the atmospheric cycles for short-lived gaseous and aerosol species have led to the development of complex models to interpret observations, test our theoretical understanding of atmospheric chemistry and predict future atmospheric composition. The validation of numerical models requires accurate information concerning the variability of atmospheric composition for targeted species via comparison with observations and measurements.In this paper, we provide an overview of recent advances in instrumentation and methodologies for measuring atmospheric composition changes from space, aircraft and the surface as well as recent improvements in laboratory techniques that permitted scientific advance in the field of atmospheric chemistry. Emphasis is given to the most promising and innovative technologies that will become operational in the near future to improve knowledge of atmospheric composition. Our current observation capacity, however, is not satisfactory to understand and predict future atmospheric composition changes, in relation to predicted climate warming. Based on the limitation of the current European observing system, we address the major gaps in a second part of the paper to explain why further developments in current observation strategies are still needed to strengthen and optimise an observing system not only capable of responding to the requirements of atmospheric services but also to newly open scientific questions.     

Management of marine cage aquaculture

Goal, Scope and Background Marine cage aquaculture produces a large amount of waste that is released directly into the environment. To effectively manage the mariculture environment, it is important to determine the carrying capacity of an aquaculture area. In many Asian countries trash fish is dominantly used in marine cage aquaculture, which contains more water than pellet feed. The traditional nutrient loading analysis is for pellet feed not for trash fish feed. So, a more critical analysis is necessary in trash fish feed culturing areas. Methods Corresponding to FCR (feed conversion rate), dry feed conversion rate (DFCR) was used to analyze the nutrient loadings from marine cage aquaculture where trash fish is used. Based on the hydrodynamic model and the mass transport model in Xiangshan Harbor, the relationship between the water quality and the waste discharged from cage aquaculture has been determined. The environmental carrying capacity of the aquaculture sea area was calculated by applying the models noted above. Results Nitrogen and phosphorus are the water quality parameters considered in this study. The simulated results show that the maximum nitrogen and phosphorus concentrations were 0.216 mg/L and 0.039 mg/L, respectively. In most of the sea area, the nutrient concentrations were higher than the water quality standard. The calculated environmental carrying capacity of nitrogen and phosphorus in Xiangshan Harbor were 1,107.37 t/yr and 134.35 t/yr, respectively. The waste generated from cage culturing in 2000 has already exceeded the environmental carrying capacity. Discussion Unconsumed feed has been identified as the most important origin of all pollutants in cage culturing systems. It suggests the importance of increasing the feed utilization and improving the feed composition on the basis of nutrient requirement. For the sustainable development of the aquaculture industry, it is an effective management measure to keep the stocking density and pollution loadings below the environmental carrying capacity. Conclusions The DFCR-based nutrient loadings analysis indicates, in trash fish feed culturing areas, that it is more critical and has been proved to be a valuable loading calculation method. The modeling approach for Xiangshan Harbor presented in this paper is a cost-effective method for assessing the environmental impact and determining the capacity. Carrying capacity information can give scientific suggestions for the sustainable management of aquaculture environments. Recommendations and Perspectives It has been proved that numerical models were convenient tools to predict the environmental carrying capacity. The development of models coupled with dynamic and aquaculture ecology is a requirement of further research. Such models can also be useful in monitoring the ecological impacts caused by mariculture activities. ESS-Submission Editor: Hailong Wang (hailong.wang@ensisjv.com)     

Characterization of mucilage aggregates in Adriatic and Tyrrhenian Sea: structure similarities between mucilage samples and the insoluble fractions of marine humic substance

The appearance of gelatinous aggregates called mucilages causes serious damages to tourism and fishery industries of the Adriatic Sea. So, many studies have been planned and some of them are still in progress to clarify the origin and causes of the phenomenon. The scientific research has showed that mucilages are produced by several marine organisms when peculiar climatic and trophic conditions occur. Moreover, as far as the mucilage composition is concerned, although it is well known that polysaccharides give a high contribution, knowledge of the structural characteristics of mucilages and their relationship with the natural organic matter of the marine environment has not been clarified yet. In this paper a study on the characterization of the marine mucilage samples collected in the Adriatic and Tyrrhenian Seas is described. The study was performed by spectroscopic (infrared and colorimetric) techniques, and elemental analysis. The results showed that mucilage samples have chemical and structural similarities with the insoluble fraction of the marine humic substance (humin). According to experimental evidences it is possible to establish the relationship between mucilages and the dissolved organic matter (DOM) in the marine environment in order to identify the most likely pathways of mucilage formation.     

Wastewater treatment to enhance the economic viability of microalgae culture

Microalgae culture is still not economically viable and it presents some negative environmental impacts, concerning water, nutrient and energy requirements. In this context, this study aims to review the recent advances on microalgal cultures in wastewaters to enhance their economic viability. We focused on three different culture concepts: (1) suspended cell systems, (2) cell immobilization, and (3) microalgae consortia. Cultures with suspended cells are the most studied. The nutrient removal efficiencies are usually high for wastewaters of different sources. However, biomass harvesting is difficult and a costly process due to the small cell size and lower culture density. On the other hand, the cell immobilization systems showed to be the solution for this problem, having as main limitation the nutrient diffusion from bulk to cells, which results in a reduced nutrient removal efficiency. The consortium between microalgae and bacteria enhances the growth of both microorganisms. This culture concept showed to be a promising technology to improve wastewater treatment, regarding not only nutrient removal but also biomass harvesting by bioflocculation. The aggregation mechanism must be studied in depth to find the process parameters that would lead to an effective and cheap harvesting process.     

Sampling and physico-chemical analysis of precipitation: a review

Wet deposition is one of two processes governing the transfer of beneficial and toxic chemicals from the atmosphere on to surfaces. Since the early 1970s, numerous investigators have sampled and analyzed precipitation for their chemical constituents, in the context of "acidic rain" and related atmospheric processes. Since then, significant advances have been made in our understanding of how to sample rain, cloud and fog water to preserve their physico-chemical integrity prior to analyses. Since the 1970s large-scale precipitation sampling networks have been in operation to broadly address regional and multi-regional issues. However, in examining the results from such efforts at a site-specific level, concerns have been raised about the accuracy and precision of the information gathered. There is mounting evidence to demonstrate the instability of precipitation samples (e.g. with N species) that have been subjected to prolonged ambient or field conditions. At the present time precipitation sampling procedures allow unrefrigerated or refrigerated collection of wet deposition from individual events, sequential fractions within events, in situ continuous chemical analyses in the field and even sampling of single or individual rain, cloud and fog droplets. Similarly analytical procedures of precipitation composition have advanced from time-consuming methods to rapid and simultaneous analyses of major anions and cations, from bulk samples to single droplets. For example, analytical techniques have evolved from colorimetry to ion chromatography to capillary electrophoresis. Overall, these advances allow a better understanding of heterogeneous reactions and atmospheric pollutant scavenging processes by precipitation. In addition, from an environmental perspective, these advances allow better quantification of semi-labile (e.g. NH4+, frequently its deposition values are underestimated) or labile species [e.g. S (IV)] in precipitation and measurements of toxic chemicals such as Hg and PCBs (polychlorinated biphenyls). Similarly, methods now exist for source-receptor studies, using for example, the characterization of reduced elemental states and/or the use of stable isotopes in precipitation as tracers. Future studies on the relationship between atmospheric deposition and environmental impacts must exploit these advances. This review provides a comprehensive and comparative treatment of the state of the art sampling methods of precipitation and its physico-chemical analysis.     

Mineralogy, morphology, and textural relationships in coatings on quartz grains in sediments in a quartz-sand aquifer

Mineralogical studies of coatings on quartz grains and bulk sediments from an aquifer on Western Cape Cod, Massachusetts, USA were carried out using a variety of transmission electron microscopy (TEM) techniques. Previous studies demonstrated that coatings on quartz grains control the adsorption properties of these sediments. Samples for TEM characterization were made by a gentle mechanical grinding method and focused ion beam (FIB) milling. The former method can make abundant electron-transparent coating assemblages for comprehensive and quantitative X-ray analysis and the latter technique protects the coating texture from being destroyed. Characterization of the samples from both a pristine area and an area heavily impacted by wastewater discharge shows similar coating textures and chemical compositions. Major constituents of the coating include Al-substituted goethite and illite/chlorite clays. Goethite is aggregated into well-crystallized domains through oriented attachment resulting in increased porosity. Illite/chlorite clays with various chemical compositions were observed to be mixed with goethite aggregates and aligned sub-parallel to the associated quartz surface. The uniform spatial distribution of wastewater-derived phosphorus throughout the coating from the wastewater-contaminated site suggests that all of the coating constituents, including those adjacent to the quartz surface, are accessible to groundwater solutes. Both TEM characterization and chemical extraction results indicate there is a significantly greater amount of amorphous iron oxide in samples from wastewater discharge area compared to those from the pristine region, which might reflect the impact of redox cycling of iron under the wastewater-discharge area. Coating compositions are consistent with the moderate metal and oxy-metalloid adsorption capacities, low but significant cation exchange capacities, and control of iron(III) solubility by goethite observed in reactive transport experimental and modeling studies conducted at the site.     

Biogeochemical Control of the Coupled CO2–O2 System of the Baltic Sea: A Review of the Results of Baltic-C

Past, present, and possible future changes in the Baltic Sea acid–base and oxygen balances were studied using different numerical experiments and a catchment–sea model system in several scenarios including business as usual, medium scenario, and the Baltic Sea Action Plan. New CO₂ partial pressure data provided guidance for improving the marine biogeochemical model. Continuous CO₂ and nutrient measurements with high temporal resolution helped disentangle the biogeochemical processes. These data and modeling indicate that traditional understandings of the nutrient availability–organic matter production relationship do not necessarily apply to the Baltic Sea. Modeling indicates that increased nutrient loads will not inhibit future Baltic Sea acidification; instead, increased mineralization and biological production will amplify the seasonal surface pH cycle. The direction and magnitude of future pH changes are mainly controlled by atmospheric CO₂ concentration. Apart from decreasing pH, we project a decreasing calcium carbonate saturation state and increasing hypoxic area.     

Nutrient dynamics and the eutrophication of shallow lakes Kasumigaura (Japan), Donghu (PR China), and Okeechobee (USA)

We compared the nutrient dynamics of three lakes that have been heavily influenced by point and non-point source pollution and other human activities. The lakes, located in Japan (Lake Kasumigaura), People's Republic of China (Lake Donghu), and the USA (Lake Okeechobee), all are relatively large (> 30 km2), very shallow (< 4 m mean depth), and eutrophic. In all three lakes we found strong interactions among the sediments, water column, and human activities. Important processes affecting nutrient dynamics included nitrogen fixation, light limitation due to resuspended sediments, and intense grazing on algae by cultured fish. As a result of these complex interactions, simple empirical models developed to predict in-lake responses of total phosphorus and algal biomass to external nutrient loads must be used with caution. While published models may provide 'good' results, in terms of model output matching actual data, this may not be due to accurate representation of lake processes in the models. The variable nutrient dynamics that we observed among the three study lakes appears to be typical for shallow lake systems. This indicates that a greater reliance on lake-specific research may be required for effective management, and a lesser role of inter-lake generalization than is possible for deeper, dimictic lake systems. Furthermore, accurate predictions of management impacts in shallow eutrophic lakes may require the use of relatively complex deterministic modeling tools.     

Modeling integrated urban water systems in developing countries: case study of Port Vila,Vanuatu

Developing countries struggle to provide adequate urban water services, failing to match infrastructure with urban expansion. Despite requiring an improved understanding of alternative infrastructure performance when considering future investments, integrated modeling of urban water systems is infrequent in developing contexts. This paper presents an integrated modeling methodology that can assist strategic planning processes, using Port Vila, Vanuatu, as a case study. 49 future model scenarios designed for the year 2050, developed through extensive stakeholder participation, were modeled with UVQ (Urban Volume and Quality). The results were contrasted with a 2015 model based on current infrastructure, climate, and water demand patterns. Analysis demonstrated that alternative water servicing approaches can reduce Port Vila’s water demand by 35 %, stormwater generation by 38 %, and nutrient release by 80 % in comparison to providing no infrastructural development. This paper demonstrates that traditional centralized infrastructure will not solve the wastewater and stormwater challenges facing rapidly growing urban cities in developing countries.     

Chemical and physical analyses of Houston aerosol for interlaboratory comparison of source apportionment procedures

Eighteen consecutive 12-h ambient aerosol samples were obtained in Houston, TX, as part of a U.S. Environmental Protection Agency visibility study in that city. The samples were collected on Teflon, Nuclepore and quartz filters by means of dichotomous samplers and were analyzed for mass, elemental and ionic species concentrations by β-ray attenuation. X-ray fluorescence, ion chromatography, colorimetry, instrumental neutron activation analysis and pyrolysis. The specimens and analytical data were distributed to participants of the Mathematical and Empirical Receptor Models Workshop (Quail Roost II), to provide a basis for comparison of source apportionment procedures. Certain workshop participants undertook further analyses of the specimens by X-ray powder diffraction, scanning electron microscopy with automated image analysis and X-ray energy spectroscopy and analytical light microscopy. This report describes all of these analytical procedures. Also, through prototype comparison mechanisms, the elemental, compound and individual particle data are reduced to a common basis (elemental composition), permitting intercomparisons of results from different methods. In general, the intercomparisons suggest that each analytical technique has certain advantages and limitations for receptor modeling and that the various techniques are best viewed as complimentary. Combinations of analytical approaches can lead to improved source resolution in the apportionment calculations.     

Updated methods for assessing the impacts of nearby gas drilling and production on neighborhood air quality and human health

An explosive growth in natural gas production within the last decade has fueled concern over the public health impacts of air pollutant emissions from oil and gas sites in the Barnett and Eagle Ford shale regions of Texas. Commonly acknowledged sources of uncertainty are the lack of sustained monitoring of ambient concentrations of pollutants associated with gas mining, poor quantification of their emissions, and inability to correlate health symptoms with specific emission events. These uncertainties are best addressed not by conventional monitoring and modeling technology, but by increasingly available advanced techniques for real-time mobile monitoring, microscale modeling and source attribution, and real-time broadcasting of air quality and human health data over the World Wide Web. The combination of contemporary scientific and social media approaches can be used to develop a strategy to detect and quantify emission events from oil and gas facilities, alert nearby residents of these events, and collect associated human health data, all in real time or near-real time. The various technical elements of this strategy are demonstrated based on the results of past, current, and planned future monitoring studies in the Barnett and Eagle Ford shale regions.

Implications: Resources should not be invested in expanding the conventional air quality monitoring network in the vicinity of oil and gas exploration and production sites. Rather, more contemporary monitoring and data analysis techniques should take the place of older methods to better protect the health of nearby residents and maintain the integrity of the surrounding environment.