Marine and farmed fish on the Polish market: comparison of the nutritive value and human exposure to PCDD/Fs and other contaminants

Chemical analyses were performed in nine fish species that are popular on the Polish market. These included Baltic fish (cod, herring, salmon), fish farmed in Poland (carp, trout), marine fish imported from China (Alaska pollock, sole), and farmed fish imported from Vietnam and China (sutchi catfish, tilapia). The nutritional composition (amino acid, micro- and macronutrients, fat-soluble vitamins - A₁, D₃, E) and certain contaminants (organochlorine pesticides, OCPs; indicator polychlorinated biphenyl, PCB₆; polychlorinated dibenzo-paradioxins and polychlorinated dibenzofurans, PCDD/Fs; dioxin-like polychlorinated biphenyls, dl-PCBs; organotin compounds, OCTs; dyes, malachite green and crystal violet; veterinary drug residues, nitrofurans and chloramphenicol; toxic metals, Cd, Pb, Hg) in the muscle tissues of fish were determined. It was confirmed that the fish species analyzed were excellent sources of amino acids, and were rich in phosphorous and selenium. Baltic Sea fish (salmon, herring), fish farmed in Poland (carp and trout), and tilapia were also rich in vitamin D₃.Traces of OCP, PCB₆, OCT, dyes, veterinary drug residues, and heavy metals were detected in concentrations which do not pose a threat to consumers at the current rate of fish consumption in Poland. However, the problem might arise from the content of PCDD/Fs and dl-PCBs in fatty Baltic fish. The fish species analyzed, differed in their nutritional values and degrees of contamination. We suggest that for optimum health and safety, it is advisable that consumers include a variety of different fish species in their diets.     

Integrated evaluation of the performance of a more than seven year old permeable reactive barrier at a site contaminated with chlorinated aliphatic hydrocarbons (CAHs)

An important issue of concern for permeable reactive iron barriers is the long-term efficiency of the barriers due to the long operational periods required. Mineral precipitation resulting from the anaerobic corrosion of the iron filings and bacteria present in the barrier may play an important role in the long-term performance. An integrated study was performed on the Vapokon permeable reactive barrier (PRB) in Denmark by groundwater and iron core sample characterization. The detailed field groundwater sampling carried out from more than 75 well screens up and downstream the barrier showed a very efficient removal (>99%) for the most important CAHs (PCE, TCE and 1,1,1-TCA). However, significant formation of cis-DCE within the PRB resulted in an overall insufficient efficiency for cis-DCE removal. The detailed analysis of the upstream groundwater revealed a very heterogeneous spatial distribution of contaminant loading into the PRB, which resulted in that only about a quarter of the barrier system is treating significant loads of CAHs. Laboratory batch experiments using contaminated groundwater from the site and iron material from the core samples revealed that the aged iron material performed equally well as virgin granular iron of the same type based on determined degradation rates despite that parts of the cored iron material were covered by mineral precipitates (especially iron sulfides, carbonate green rust and aragonite). The PCR analysis performed on the iron core samples indicated the presence of a microbial consortium in the barrier. A wide range of species were identified including sulfate and iron reducing bacteria, together with Dehalococcoides and Desulfuromonas species indicating microbial reductive dehalogenation potential. The microbes had a profound effect on the performance of the barrier, as indicated by significant degradation of dichloromethane (which is typically unaffected by zero valent iron) within the barrier.     

Characterisation and fingerprinting of PCBs in flue gas and ash from waste incineration and in technical mixtures

Congener patterns of mono- to deca-chlorinated biphenyls (PC1-10B) were evaluated in (a) waste incineration flue gases collected in the post-combustion zone of a laboratory-scale fluidized-bed reactor, (b) ashes from two different MSW incineration plants, and (c) published data of eight Aroclor formulations. The congener patterns of the flue gases, ashes, and Aroclor mixtures clearly differed from each other, likely reflecting differences in formation pathways. The flue gas congener patterns were largely dominated by the least chlorinated congeners, whereas the ashes displayed more evenly distributed patterns. The most abundant congeners indicated a preference for 3,3',4,4'-oriented substitution, which may be related to de novo-type formation involving perylene. Principal component analysis confirmed that congener patterns differed among the three matrices and also distinguished flue gases collected at 200 °C from those collected at 300 °C and 450 °C. This distinction could be partly explained by the degree of chlorination, although the substitution status of the ortho-position, and substitution in the 3,3',4,4'-positions also seemed to be influential. Injecting biphenyl into the post-combustion zone of the reactor did not alter the patterns, indicating that availability of the backbone structure is not a limiting factor for PCB formation.     

Comparing universal kriging and land-use regression for predicting concentrations of gaseous oxides of nitrogen (NOx) for the Multi-Ethnic Study of Atherosclerosis and Air Pollution (MESA Air)

BACKGROUND: Epidemiological studies that assess the health effects of long-term exposure to ambient air pollution are used to inform public policy. These studies rely on exposure models that use data collected from pollution monitoring sites to predict exposures at subject locations. Land use regression (LUR) and universal kriging (UK) have been suggested as potential prediction methods. We evaluate these approaches on a dataset including measurements from three seasons in Los Angeles, CA. METHODS: The measurements of gaseous oxides of nitrogen (NOx) used in this study are from a "snapshot" sampling campaign that is part of the Multi-Ethnic Study of Atherosclerosis and Air Pollution (MESA Air). The measurements in Los Angeles were collected during three two-week periods in the summer, autumn, and winter, each with about 150 sites. The design included clusters of monitors on either side of busy roads to capture near-field gradients of traffic-related pollution. LUR and UK prediction models were created using geographic information system (GIS)-based covariates. Selection of covariates was based on 10-fold cross-validated (CV) R(2) and root mean square error (RMSE). Since UK requires specialized software, a computationally simpler two-step procedure was also employed to approximate fitting the UK model using readily available regression and GIS software. RESULTS: UK models consistently performed as well as or better than the analogous LUR models. The best CV R(2) values for season-specific UK models predicting log(NOx) were 0.75, 0.72, and 0.74 (CV RMSE 0.20, 0.17, and 0.15) for summer, autumn, and winter, respectively. The best CV R(2) values for season-specific LUR models predicting log(NOx) were 0.74, 0.60, and 0.67 (CV RMSE 0.20, 0.20, and 0.17). The two-stage approximation to UK also performed better than LUR and nearly as well as the full UK model with CV R(2) values 0.75, 0.70, and 0.70 (CV RMSE 0.20, 0.17, and 0.17) for summer, autumn, and winter, respectively. CONCLUSION: High quality LUR and UK prediction models for NOx in Los Angeles were developed for the three seasons based on data collected for MESA Air. In our study, UK consistently outperformed LUR. Similarly, the 2-step approach was more effective than the LUR models, with performance equal to or slightly worse than UK.     

Characterization of PM(2.5) collected during broadcast and slash-pile prescribed burns of predominately ponderosa pine forests in northern Arizona

Prescribed burning, in combination with mechanical thinning, is a successful method for reducing heavy fuel loads from forest floors and thereby lowering the risk of catastrophic wildfire. However, an undesirable consequence of managed fire is the production of fine particulate matter or PM(2.5) (particles ≤2.5 μm in aerodynamic diameter). Wood-smoke particulate data from 21 prescribed burns are described, including results from broadcast and slash-pile burns. All PM(2.5) samples were collected in situ on day 1 (ignition) or day 2. Samples were analyzed for mass, polycyclic aromatic hydrocarbons (PAHs), inorganic elements, organic carbon (OC), and elemental carbon (EC). Results were characteristic of low intensity, smoldering fires. PM(2.5) concentrations varied from 523 to 8357 μg m(-3) and were higher on day 1. PAH weight percents (19 PAHs) were higher in slash-pile burns (0.21 ± 0.08% OC) than broadcast burns (0.07 ± 0.03% OC). The major elements were K, Cl, S, and Si. OC and EC values averaged 66 ± 7 and 2.8 ± 1.4% PM(2.5), respectively, for all burns studied, in good agreement with literature values for smoldering fires.     

Optimal deployment of emissions reduction technologies for construction equipment

The objective of this research was to develop a multiobjective optimization model to deploy emissions reduction technologies for nonroad construction equipment to reduce emissions in a cost-effective and optimal manner. Given a fleet of construction equipment emitting different pollutants in the nonattainment (NA) and near -nonattainment (NNA) counties of a state and a set of emissions reduction technologies available for installation on equipment to control pollution/emissions, the model assists in determining the mix of technologies to be deployed so that maximum emissions reduction and fuel savings are achieved within a given budget. Three technologies considered for emissions reduction were designated as X, Y, and Z to keep the model formulation general so that it can be applied for any other set of technologies. Two alternative methods of deploying these technologies on a fleet of equipment were investigated with the methods differing in the technology deployment preference in the NA and NNA counties. The model having a weighted objective function containing emissions reduction benefits and fuel-saving benefits was programmed with C++ and ILOG-CPLEX. For demonstration purposes, the model was applied for a selected construction equipment fleet owned by the Texas Department of Transportation, located in NA and NNA counties of Texas, assuming the three emissions reduction technologies X, Y, and Z to represent, respectively, hydrogen enrichment, selective catalytic reduction, and fuel additive technologies. Model solutions were obtained for varying budget amounts to test the sensitivity of emissions reductions and fuel-savings benefits with increasing the budget. Different mixes of technologies producing maximum oxides of nitrogen (NO(x)) reductions and total combined benefits (emissions reductions plus fuel savings) were indicated at different budget ranges. The initial steep portion of the plots for NO(x) reductions and total combined benefits against budgets for different combinations of emissions reduction technologies indicated a high benefit-cost ratio at lower budget amounts. The rate of NO(x) reductions and the increase of combined benefits decreased with increasing the budget, and with the budget exceeding certain limits neither further NO(x) reductions nor increased combined benefits were observed. Finally, the Pareto front obtained would enable the decision-maker to achieve a noninferior optimal combination of total NO(x) reductions and fuel-savings benefits for a given budget.     

Investigation of solution chemistry effects on sorption behavior of Cu(II) on ZSM-5 zeolite

The sorption of Cu(II) from an aqueous solution using ZSM-5 zeolite was investigated by batch technique under ambient conditions. Sorption was investigated as a function of pH, ionic strength, foreign ions, humic substances, and temperature. The results indicate that the sorption of Cu(II) on ZSM-5 zeolite is strongly dependent on pH. Sorption is dependent on ionic strength at low pH, but independent of ionic strength at high pH values. The presence of humic/fluvic acid (HA/FA) enhances the sorption of Cu(II) on ZSM-5 zeolite at low pH values, and reduces Cu(II) sorption at high pH values. Sorption isotherms were well simulated by the Langmuir model. Thermodynamic parameters (i.e., deltaH0, deltaS0 and deltaG0) for the sorption of Cu(II) were determined from temperature-dependent sorption isotherms at 293.15, 313.15, and 333.15 K, respectively. Results indicate that the sorption process of Cu(II) on ZSM-5 zeolite is spontaneous and endothermic.     

Internally mixed sea salt, soot, and sulfates at Macao, a coastal city in South China

Direct observation of the mixing state of aerosol particles in a coastal urban city is critical to understand atmospheric processing and hygroscopic growth in humid air. Morphology, composition, and mixing state of individual aerosol particles from Macao, located south of the Pearl River Delta (PRD) and 100 km west of Hong Kong, were investigated using scanning electron microscopy (SEM) and transmission electron microscopy coupled with energy-dispersive X-ray spectrometry (TEM/EDX). SEM images show that soot and roughly spherical particles are prevalent in the samples. Based on the compositions of individual aerosol particles, aerosol particles with roughly spherical shape are classified into coarse Na-rich and fine S-rich particles. TEM/EDX indicates that each Na-rich particle consists of a Na-S core and NaNO3 shell. Even in the absence of heavy pollution, the marine sea salt particles were completely depleted in chloride, and Na-related sulfates and nitrates were enriched in Macao air. The reason could be that SO2 from the polluted PRD and ships in the South China Sea and NO2 from vehicles in the city sped up the chlorine depletion in sea salt through heterogeneous reactions. Fresh soot particles from vehicular emissions mainly occur near curbside. However, there are many aged soot particles in the sampling site surrounded by main roads 200 to 400 m away, suggesting that the fresh soot likely underwent a quick aging. Overall, secondary nitrates and sulfates internally mixed with soot and sea salt particles can totally change their surface hygroscopicity in coastal cities.     

A hybrid method for quasi-three-dimensional slope stability analysis in a municipal solid waste landfill

Limited space for accommodating the ever increasing mounds of municipal solid waste (MSW) demands the capacity of MSW landfill be maximized by building landfills to greater heights with steeper slopes. This situation has raised concerns regarding the stability of high MSW landfills. A hybrid method for quasi-three-dimensional slope stability analysis based on the finite element stress analysis was applied in a case study at a MSW landfill in north-east Spain. Potential slides can be assumed to be located within the waste mass due to the lack of weak foundation soils and geosynthetic membranes at the landfill base. The only triggering factor of deep-seated slope failure is the higher leachate level and the relatively high and steep slope in the front. The valley-shaped geometry and layered construction procedure at the site make three-dimensional slope stability analyses necessary for this landfill. In the finite element stress analysis, variations of leachate level during construction and continuous settlement of the landfill were taken into account. The "equivalent" three-dimensional factor of safety (FoS) was computed from the individual result of the two-dimensional analysis for a series of evenly spaced cross sections within the potential sliding body. Results indicate that the hybrid method for quasi-three-dimensional slope stability analysis adopted in this paper is capable of locating roughly the spatial position of the potential sliding mass. This easy to manipulate method can serve as an engineering tool in the preliminary estimate of the FoS as well as the approximate position and extent of the potential sliding mass. The result that FoS obtained from three-dimensional analysis increases as much as 50% compared to that from two-dimensional analysis implies the significance of the three-dimensional effect for this study-case. Influences of shear parameters, time elapse after landfill closure, leachate level as well as unit weight of waste on FoS were also investigated in this paper. These sensitivity analyses serve as the guidelines of construction practices and operating procedures for the MSW landfill under study.