Evaluation of gas emissions from coal stockpile

Gas emissions of carbon dioxide, methane, dimethylsulfide, carbon monoxide and oxygen from a coal stockpile in Velenje were determined. Gases from the coal stockpile were collected in Alltech Standard sampling bags and then analysed using a capillary gas chromatograph and electrochemical sensors. A flame ionisation detector equipped with a Zr/Ni catalytic reactor was used for the determination of methane and carbon dioxide. Dimethylsulfide was detected with a flame photometric detector, and the concentrations of carbon monoxide and oxygen were determined by use of electrochemical sensors. The results showed that the main influence on gas emissions is related to the ambient temperature. Emissions of carbon dioxide during summer 2001 (average temperature during sampling period was 24 degrees C) were approximately 30-times higher than during winter 2002 (average temperature during sampling period was -2 degrees C) and were also influenced by the oxygen concentration. Carbon dioxide is mainly formed by oxidation of coal. Methane and dimethylsulfide are desorbed from coal, and are present in higher concentrations in stockpile emissions when stockpiles are renewed. The dimethylsulfide concentration, in contrast to laboratory experiments in stockpile emissions, falls immediately due to photo-degradation.     

Numerical modeling of flow structures over various flat-topped stockpiles height: Implications on dust emissions

Fugitive dust emissions from open stock yards for bulk materials, such as coal or ores, can represent a significant part of overall estimated atmospheric emission on industrial site, as example on steel plant sites. Stockpile topography is known to modify the near field uptake force of the wind through changes of the mean flow. Various studies have shown that aeolian erosion strongly occurs on the stockpile crest, so it appears relevant to carry out a study to analyze the effect on the dust emissions of the stockpile clipping. Three-dimensional numerical simulations were done with the aim of simulating wind flow over different flat-topped pile scenarios, corresponding to a constant material volume. Various wind flow directions were tested to determine its impact on particle emissions. Data obtained from Computational Fluid Dynamics simulations were then integrated in order to estimate the effect of the clipping on the stockpiles dust emission rates by using the EPA's emission factors method. Results provide evidence to suggest that clipping stockpiles does not reduce dust emissions. This study provides to industrial operators some informations on the best geometrical pile characteristics in order to limit particles emissions.     

A multi-stage sampling strategy for the delineation of soil pollution in a contaminated brownfield

A multi-stage sampling strategy, based on sequential Gaussian simulation, was presented to optimize the step-wise selection of a small numbers of additional samples to delineate soil pollution. This strategy was applied to a Belgian brownfield of 5.2 ha polluted with lead (Pb). Starting from an initial number of 240 samples in stage 1, additional samples were added, 25 per stage, and the reduction of the uncertainty in the Pb delineation was monitored. Twenty stages were used. Already in stage 6 a local optimum was found based on the median conditional coefficient of variation. An independent validation confirmed that this index was to be preferred over the median conditional variance. So for the brownfield considered our procedure indicated that 365 selected samples would have been sufficient, representing a gain of 70.7% in sampling effort compared to current practice which resulted in a sampling effort of 1245 samples.     

Small-scale variability of metals in soil and composite sampling

Soil pollution data is also strongly scattering at small scale. Sampling of composite samples, therefore, is recommended for pollution assessment. Different statistical methods are available to provide information about the accuracy of the sampling process. Autocorrelation and variogram analysis can be applied to investigate spatial relationships. Analysis of variance is a useful method for homogeneity testing. The main source of the total measurement uncertainty is the uncertainty arising from sampling. The sample mass required for analysis can also be estimated using an analysis of variance. The number of increments to be taken for a composite sample can be estimated by means of simple statistical formulae. Analytical results of composite samples obtained from different fusion procedures of increments can be compared by means of multiple mean comparison. The applicability of statistical methods and their advantages are demonstrated for a case study investigating metals in soil at a very small spatial scale. The paper describes important statistical tools for the quantitative assessment of the sampling process. Detailed results clearly depend on the purpose of sampling, the spatial scale of the object under investigation and the specific case study, and have to be determined for each particular case.     

Influence of pre-treatment step on PAHs analyses in contaminated soils

There is no specific standardization for the pre-treatment of a soil sample for PAHs analyses. The ISO/FDIS 14507 method for soil quality gives a guidance for sample pre-treatment before measurement of organic contaminants in soil. It refers to cryogenic crushing which is not so easy to carry out. So, analysts lead to develop in house methods which can be very different from a laboratory to another and can involve deviations in the pollution quantification. This study has explored different ways of drying, grinding and sieving in order to determine the influence of the soil sample handling on the measured pollutant concentration. It appears that the influence of pre-treatment depends on the soil nature and on the PAHs distribution. As a conclusion, it is advised "light" drying ways like air drying or drying at 40 degrees C in a drying oven instead of more "drastic" ways (freeze-drying, cryogenic crushing) which can induce some losses. Crushing and sieving are also recommended for more reproducible measures.     

Comparisons of particulate-bound mercury (PBM) compositions in soil and vegetation at a traffic site

This investigation analyzes the particulate-bound mercury (PBM) compositions in soil and vegetation at a traffic sampling site in Taichung, Taiwan, during a sampling period from October to December, 2015. A direct mercury analyzer (DMA-80) was used to measure the particulate-bound mercury (PBM). A T-test was conducted to determine the mean differences between the PBM composition in soil and that in vegetation at the site. The results indicate that 1) the mean particulate-bound mercury compositions in soil and vegetation were the lowest in November, when the (mean OR average) wind speed was the highest (4.1 m/s); 2) Particulate-bound mercury compositions (PBM) in both soil and vegetation correlated weakly with temperature, humidity and wind speed; 3) T-test statistical results denoted that the PBM compositions did not significantly differ between soil and vegetation in the three-month sampling period.     

The potential of diffuse reflectance spectroscopy for the determination of carbon inventories in soils

Investigations have shown that near- and mid-infrared reflectance spectroscopy can accurately determine organic-C in soil. Efforts have also demonstrated that both can differentiate between organic and inorganic-C in soils, but the mid-infrared produces more accurate calibrations. Nevertheless, the greatest benefit would come with in situ determinations where factors such as particle size, sample heterogeneity and moisture can be important. While the variations in large (> 20 mesh) particle size can adversely effect calibration accuracy, efforts have demonstrated that the scanning of larger amounts of sample can overcome this, but the effects of moisture have not been fully explored. While under in situ conditions C distribution and sample heterogeneity are a problem for any analytical method, the rapid analysis possible with spectroscopic techniques will allow many more samples to be analyzed. In conclusion, near- and mid-infrared spectroscopy have great potential for providing the C values needed for C sequestration studies.     

DNAPL distribution in the source zone: effect of soil structure and uncertainty reduction with increased sampling density

This paper focuses on parameters describing the distribution of dense nonaqueous phase liquid (DNAPL) contaminants and investigates the variability of these parameters that results from soil heterogeneity. In addition, it quantifies the uncertainty reduction that can be achieved with increased density of soil sampling. Numerical simulations of DNAPL releases were performed using stochastic realizations of hydraulic conductivity fields generated with the same geostatistical parameters and conditioning data at two sampling densities, thus generating two simulation ensembles of low and high density (three-fold increase) of soil sampling. The results showed that DNAPL plumes in aquifers identical in a statistical sense exhibit qualitatively different patterns, ranging from compact to finger-like. The corresponding quantitative differences were expressed by defining several alternative measures that describe the DNAPL plume and computing these measures for each simulation of the two ensembles. The uncertainty in the plume features under study was affected to different degrees by the variability of the soil, with coefficients of variation ranging from about 20% to 90%, for the low-density sampling. Meanwhile, the increased soil sampling frequency resulted in reductions of uncertainty varying from 7% to 69%, for low- and high-uncertainty variables, respectively. In view of the varying uncertainty in the characteristics of a DNAPL plume, remedial designs that require estimates of the less uncertain features of the plume may be preferred over others that need a more detailed characterization of the source zone architecture.     

Protocol Development for Assessing Arsenic Background Concentrations in Florida Urban Soils

Knowledge of arsenic background concentrations in urban soils is important for making remediation decisions. The soil cleanup target level (SCTL) for arsenic in Florida lies within the range of arsenic background concentrations. The residential SCTL is also near the practical quantification limits using analytical procedures. Currently no standard protocols are available for determining arsenic background concentrations in urban soils, apart from site-specific cases. Therefore, a pilot study was conducted to develop and employ appropriate protocols to determine arsenic distribution in urban soils. This involved: site selection (e.g. size and sampling frame), sample collection (e.g. sampling technique), and statistical considerations (e.g. design). Factors such as ease of sample collection and maintaining anonymity of private properties were also considered as they influence the successful implementation of the study. Forty surface soil samples each were collected from five categories in three land use classes (residential-yard and right-of-way, commercial and public land-parks and public building), digested using EPA method 3051a and analysed using graphite furnace atomic absorption spectrometry. Experiences from the pilot study (e.g. complications during sample selection, digestion, data censoring etc.) were used in the development of the final protocol to be used in determining the distribution of arsenic in urban areas.     

Protocol Development for Assessing Arsenic Background Concentrations in Florida Urban Soils

Knowledge of arsenic background concentrations in urban soils is important for making remediation decisions. The soil cleanup target level (SCTL) for arsenic in Florida lies within the range of arsenic background concentrations. The residential SCTL is also near the practical quantification limits using analytical procedures. Currently no standard protocols are available for determining arsenic background concentrations in urban soils, apart from site-specific cases. Therefore, a pilot study was conducted to develop and employ appropriate protocols to determine arsenic distribution in urban soils. This involved: site selection (e.g. size and sampling frame), sample collection (e.g. sampling technique), and statistical considerations (e.g. design). Factors such as ease of sample collection and maintaining anonymity of private properties were also considered as they influence the successful implementation of the study. Forty surface soil samples each were collected from five categories in three land use classes (residential-yard and right-of-way, commercial and public land-parks and public building), digested using EPA method 3051a and analysed using graphite furnace atomic absorption spectrometry. Experiences from the pilot study (e.g. complications during sample selection, digestion, data censoring etc.) were used in the development of the final protocol to be used in determining the distribution of arsenic in urban areas.     

Decision support tool for soil sampling of heterogeneous pesticide (chlordecone) pollution

When field pollution is heterogeneous due to localized pesticide application, as is the case of chlordecone (CLD), the mean level of pollution is difficult to assess. Our objective was to design a decision support tool to optimize soil sampling. We analyzed the CLD heterogeneity of soil content at 0–30- and 30–60-cm depth. This was done within and between nine plots (0.4 to 1.8 ha) on andosol and ferralsol. We determined that 20 pooled subsamples per plot were a satisfactory compromise with respect to both cost and accuracy. Globally, CLD content was greater for andosols and the upper soil horizon (0–30 cm). Soil organic carbon cannot account for CLD intra-field variability. Cropping systems and tillage practices influence the CLD content and distribution; that is CLD pollution was higher under intensive banana cropping systems and, while upper soil horizon was more polluted than the lower one with shallow tillage (<40 cm), deeper tillage led to a homogenization and a dilution of the pollution in the soil profile. The decision tool we proposed compiles and organizes these results to better assess CLD soil pollution in terms of sampling depth, distance, and unit at field scale. It accounts for sampling objectives, farming practices (cropping system, tillage), type of soil, and topographical characteristics (slope) to design a relevant sampling plan. This decision support tool is also adaptable to other types of heterogeneous agricultural pollution at field level.     

The Forum of the International HCH and Pesticides Association—a platform for international cooperation

The unsustainable life cycle management of pesticides in the last 60 years has created large pesticide stockpiles. The two major working areas of the International HCH and Pesticide Association (IHPA; www.ihpa.info) address a part of these legacies and are shortly introduced here: (1) The assessment and support of the management of the worlds single largest POPs stockpile: the globally dumped 4 to 7 million tonnes hexachlorocyclohexane (HCH) wastes from lindane production, and (2) the support for the management of the obsolete pesticides legacy in Eastern Europe, the Caucasus and Central Asia (EECCA) countries of ~240,000 t, leaving these pesticides in unregulated storages without adequate safety control being a huge risk to the environment and human health. The integrative approach IHPA takes—promoting international cooperation and the exchange of knowledge and experiences—is shortly explained. IHPA has developed various supporting tools for its work: the IHPA web page and newsletter informing on the threats and challenges, but also on the progresses of managing pesticide stockpiles; the joint GIZ-PAN-IHPA exhibition on awareness of the pesticide stockpile challenge; and the ‘International HCH and Pesticides Forum’ as most important tool to progress the integrative work and mission of IHPA. Finally, a summary of the 11th International HCH and Pesticides Forum held in Gabala, Azerbaijan is given which brought together more than 120 scientists, policy-makers, non-governmental and international organisations, industry and students from more than 40 countries to progress the obsolete pesticides and hazardous chemical waste challenge in EECCA countries. The event finished with adoption of ‘Gabala Declaration’, which aims to mobilise efforts of all stakeholders for prevention and elimination of POPs, obsolete pesticides, and hazardous chemical waste in the region.     

Effects of particulate explosives on estimating contamination at a historical explosives testing area.

A historical explosives testing area harbored contamination as unevenly distributed solid particles within a contaminant-stained soil matrix. Particles larger than 3 mm diameter accounted for 96.4% of the explosives contamination. Independent sampling and analysis methods showed significant differences in contaminant estimations due to particulate explosives. We present a solvent-based sample averaging method designed to solve spatial heterogeneity problems resulting from the presence of contaminant particles.     

Greenhouse gas emissions from dairy open lot and manure stockpile in northern China: A case study

The open lots and manure stockpiles of dairy farm are major sources of greenhouse gas (GHG) emissions in typical dairy cow housing and manure management system in China. GHG (CO₂, CH₄ and N₂O) emissions from the ground level of brick-paved open lots and uncovered manure stockpiles were estimated according to the field measurements of a typical dairy farm in Beijing by closed chambers in four consecutive seasons. Location variation and manure removal strategy impacts were assessed on GHG emissions from the open lots. Estimated CO₂, CH₄ and N₂O emissions from the ground level of the open lots were 137.5±64.7 kg hd^-1 yr^-1, 0.45±0.21 kg hd^-1 yr^-1 and 0.13±0.08 kg hd^-1 yr^-1, respectively. There were remarkable location variations of GHG emissions from different zones (cubicle zone vs. aisle zone) of the open lot. However, the emissions from the whole open lot were less affected by the locations. After manure removal, lower CH₄ but higher N₂O emitted from the open lot. Estimated CO₂, CH₄ and N₂O emissions from stockpile with a stacking height of 55±12 cm were 858.9±375.8 kg hd^-1 yr^-1, 8.5±5.4 kg hd^-1 yr^-1 and 2.3±1.1 kg hd^-1 yr^-1, respectively. In situ storage duration, which estimated by manure volatile solid contents (VS), would affect GHG emissions from stockpiles. Much higher N₂O was emitted from stockpiles in summer due to longer manure storage.

Implications: This study deals with greenhouse gas (GHG) emissions from open lots and stockpiles. It’s an increasing area of concern in some livestock producing countries. The Intergovernmental Panel on Climate Change (IPCC) methodology is commonly used for estimation of national GHG emission inventories. There is a shortage of on-farm information to evaluate the accuracy of these equations and default emission factors. This work provides valuable information for improving accounting practices within China or for similar manure management practice in other countries.     

Spatially valid data of atmospheric deposition of heavy metals and nitrogen derived by moss surveys for pollution risk assessments of ecosystems

For analysing element input into ecosystems and associated risks due to atmospheric deposition, element concentrations in moss provide complementary and time-integrated data at high spatial resolution every 5 years since 1990. The paper reviews (1) minimum sample sizes needed for reliable, statistical estimation of mean values at four different spatial scales (European and national level as well as landscape-specific level covering Europe and single countries); (2) trends of heavy metal (HM) and nitrogen (N) concentrations in moss in Europe (1990–2010); (3) correlations between concentrations of HM in moss and soil specimens collected across Norway (1990–2010); and (4) canopy drip-induced site-specific variation of N concentration in moss sampled in seven European countries (1990–2013). While the minimum sample sizes on the European and national level were achieved without exception, for some ecological land classes and elements, the coverage with sampling sites should be improved. The decline in emission and subsequent atmospheric deposition of HM across Europe has resulted in decreasing HM concentrations in moss between 1990 and 2010. In contrast, hardly any changes were observed for N in moss between 2005, when N was included into the survey for the first time, and 2010. In Norway, both, the moss and the soil survey data sets, were correlated, indicating a decrease of HM concentrations in moss and soil. At the site level, the average N deposition inside of forests was almost three times higher than the average N deposition outside of forests.     

Estimation of efficiency of processing soil samples for pesticide residues analysis

The efficiency of four sample processing methods was tested with eight different types of soils representing the major proportion of cultivated soils. The principle of sampling constant was applied for characterizing the efficiency of the procedures and testing the well-mixed status of the prepared soil. The test material was 14C-labeled atrazine that enabled keeping the random error of analyses 相似文献   

Estimation of Efficiency of Processing Soil Samples for Pesticide Residues Analysis

The efficiency of four sample processing methods was tested with eight different types of soils representing the major proportion of cultivated soils. The principle of sampling constant was applied for characterizing the efficiency of the procedures and testing the well-mixed status of the prepared soil. The test material was 14C-labeled atrazine that enabled keeping the random error of analyses ≤ about 1%. Adding water to the soil proved to be the most efficient and generally applicable procedure resulting in about 6% relative sample processing uncertainty for 20 g test portions. The expected error is inversely proportional to the mass of test portion. Smashing and manual mixing of soil resulted in about four times higher uncertainty than mixing with water. Grinding of soil is applicable for dry soils only, but the test procedure applied was not suitable for estimating a typical uncertainty of processing dry soil samples. Adding dry ice did not improve the efficiency of sample processing.     

Performance testing of a multimetals continuous emissions monitor

A prototype instrument, designed for continuous monitoring of hazardous air pollutant metal emissions in the stack gases of waste incinerators and industrial furnaces, has undergone a performance evaluation that included a relative accuracy test audit. The test results confirmed the instrument's ability to accurately measure stack gas metal concentrations and thus validate the applicability of the candidate technique for compliance assurance monitoring for the specific source involved. The analytical accuracy of this system, documented during the recent test exercise, represents a significant improvement in performance relative to that previously achieved, and can be attributed with certainty to the recent implementation of a shrouded nozzle sampling system. By reducing deposition losses of particulate matter in the extracted stack gas stream to acceptable levels, presentation of a more representative sample stream to the elemental analyzer has been accomplished. The present paper discusses the design and operation of the multimetals continuous emissions monitor (MMCEM), the shrouded nozzle sampling system, and the results of recent performance testing.     

Distribution of pesticide residues in soil and uncertainty of sampling

Pesticide residues were determined in about 120 soil cores taken randomly from the top 15 cm layer of two sunflower fields about 30 days after preemergence herbicide treatments. Samples were extracted with acetone-ethyl acetate mixture and the residues were determined with GC-TSD. Residues of dimethenamid, pendimethalin, and prometryn ranged from 0.005 to 2.97 mg/kg. Their relative standard deviations (CV) were between 0.66 and 1.13. The relative frequency distributions of residues in soil cores were very similar to those observed in root and tuber vegetables grown in pesticide treated soils. Based on all available information, a typical CV of 1.00 was estimated for pesticide residues in primary soil samples (soil cores). The corresponding expectable relative uncertainty of sampling is 20% when composite samples of size 25 are taken. To obtain a reliable estimate of the average residues in the top 15 cm layer of soil of a field up to 8 independent replicate random samples should be taken. To obtain better estimate of the actual residue level of the sampled filed would be marginal if larger number of samples were taken.     

On‐target deposition of aerially applied deltamethrin

Abstract

The mean amount of deltamethrin deposited on natural substrates (i.e., soil and vegetation) in three experiments was 63, 73, and 76% of applied. Composite samples taken from 16 sites/replicate gave representative and repeatable measures of deposition. The use of Teflon discs as artificial targets to measure aerial deposition was investigated. The discs had only 34–71% mean trapping efficiency for the spray droplets. Deposition was quite variable among different sampling sites within a field (CV=73–83%). Much of this variation was caused by irregular overlapping of spray swaths.