COMPARISON OF PROCEDURES FOR IMMEDIATE CHEMICAL ANALYSIS OF CHARCOAL

ABSTRACT The climate change, the quest for sustainability and the strong environmental pressures for alternatives to traditional fossil fuels have increased the interest in the search and use of renewable energy sources. Among them stands out the biomass of charcoal coming from renewable forests, widely used as a thermal reductant in the steel industry in the detriment of the use of mineral coal coke. This study aimed to compare different operating procedures of immediate chemical analysis of charcoal. Seven essays to immediate chemical analysis were compared, spread between procedures performed by Brazilian companies and laboratories, the test described by NBR 8112 and one realized with a thermogravimetric analyzer (TGA) using the parameters of the NBR 8112. There were significant differences in the volatiles matter content and consequently in the fixed carbon contents found. The differences between the procedures and the NBR 8112 were caused by an excess burning time, a mass sample above or below the standard or inappropriate container used for burning. It observed that the TGA appraisal of the volatiles content must be carried out with a burning time equal to 2 minutes to obtain results similar to those of the NBR 8112 norm. Moreover, the ash content values were statistically identical and the particles size did not influence the differences between means.

Tabular cusum control charts of chemical variables applied to the control of surface water quality

The aim of this study was to evaluate the application possibility of tabular CUSUM control charts in the quality control of chemical variables in surface water. It was performed bibliographic and field research to collect water samples from 2003 to 2009, totaling 30 samples, some monthly and others semi-annual in order to observe the variables that regulate water quality. It was found that these charts may be applied to control the quality of river water; showing to be effective in the perception of changes during the process, especially for small samples (n=1) which there is no repetition as in this research. It was also concluded that the Mandurim River does not presents significant levels of pollution.

Water quality indicators for environmental and resistance profile of Escherichia coli strains isolated in Rio Cascavel, Paraná, Brazil

In this article it was evaluated the quality of water in the Cascavel river, in the city of Cascavel - Paraná using microbiological indicators, physical and chemical pollution and susceptibility / resistance in strains of Escherichia coli isolated antimicrobial trade. The water sampling was conducted between 2010-July and 2011-June at three points: a) near the source, b) urban area, c) rural area. The samples were analyzed for physical, chemical and microbiological variables: temperature, pH, color, turbidity, electrical conductivity, total nitrogen and total phosphorus, total coliforms (CT), fecal coliform (CTe) and Escherichia coli. Tests were also performed to nine antimicrobial commercial resistances. The variables studied indicated that the Cascavel river water was presented at disagreement with the resolution 357/2005 CONAMA (class I), ranking in the index as regular water quality. The physical, chemical and rainfall did not affect the growth of CT and CTe, with higher counts of E. coli in the urban area. The greatest resistance profiles of the strains of E. coli isolated from Cascavel river water was found in section 2, the urban area as a probable consequence of human influence on water quality.

Element speciation and behaviour in metal-rich Boreal river and estuarine systems using ultrafiltration and chemical modelling

The bioavailability of metals and their potential for environmental pollution depends not simply on total concentrations, but is to a great extent determined by their chemical form. Consequently, knowledge of aqueous metal species is essential in investigating potential metal toxicity and mobility. The overall aim of this thesis is, thus, to determine the species of major and trace elements and the size distribution among the different forms (e.g. ions, molecules and mineral particles) in selected metal-enriched Boreal river and estuarine systems by utilising filtration techniques and geochemical modelling. On the basis of the spatial physicochemical patterns found, the fractionation and complexation processes of elements (mainly related to input of humic matter and pH-change) were examined. Dissolved (<1 kDa), colloidal (1 kDa-0.45 μm) and particulate (>0.45 μm) size fractions of sulfate, organic carbon (OC) and 44 metals/metalloids were investigated in the extremely acidic Vörå River system and its estuary in W Finland, and in four river systems in SW Finland (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), largely affected by soil erosion and acid sulfate (AS) soils. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these investigated waters. One of the most important findings of this study is that the very large amounts of metals known to be released from AS soils (including Al, Ca, Cd, Co, Cu, Mg, Mn, Na, Ni, Si, U and the lanthanoids) occur and can prevail mainly in toxic forms throughout acidic river systems; as free ions and/or sulfate-complexes. This has serious effects on the biota and especially dissolved Al is expected to have acute effects on fish and other organisms, but also other potentially toxic dissolved elements (e.g. Cd, Cu, Mn and Ni) can have fatal effects on the biota in these environments. In upstream areas that are generally relatively forested (higher pH and contents of OC) fewer bioavailable elements (including Al, Cu, Ni and U) may be found due to complexation with the more abundantly occurring colloidal OC. In the rivers in SW Finland total metal concentrations were relatively high, but most of the elements occurred largely in a colloidal or particulate form and even elements expected to be very soluble (Ca, K, Mg, Na and Sr) occurred to a large extent in colloidal form. According to geochemical modelling, these patterns may only to a limited extent be explained by in-stream metal complexation/adsorption. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of AS soils, known to exist in the catchment, could be clearly distinguished in the Sirppujoki River as it had very high concentrations of a metal sequence typical of AS soils in a dissolved form (Ba, Br, Ca, Cd, Co, K, Mg, Mn, Na, Ni, Rb and Sr). In the Paimionjoki River, metal concentrations (including Ba, Cs, Fe, Hf, Pb, Rb, Si, Th, Ti, Tl and V; not typical of AS soils in the area) were high, but it was found that the main cause of this was erosion of metal bearing phyllosilicates and thus these metals occurred dominantly in less toxic colloidal and particulate fractions. In the two nearby rivers (Laajoki and Mynäjoki) there was influence of AS soils, but it was largely masked by eroded phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high background metal concentrations due to erosion. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring, or geochemical modelling based on such data, can lead to a great overestimation of the water toxicity in this environment. The potentially toxic elements that are of concern in AS soil areas will ultimately be precipitated in the recipient estuary or sea, where the acidic metalrich river water will gradually be diluted/neutralised with brackish seawater. Along such a rising pH gradient Al, Cu and U will precipitate first together with organic matter closest to the river mouth. Manganese is relatively persistent in solution and, thus, precipitates further down the estuary as Mn oxides together with elements such as Ba, Cd, Co, Cu and Ni. Iron oxides, on the contrary, are not important scavengers of metals in the estuary, they are predicted to be associated only with As and PO4.

The Environmental Status of the Port of HaminaKotka

This study is a part of the Ecologically Friendly Port Ust-Luga (EFP) project. The purpose of this study is to examine the environmental status of the Finnish ports and, more specifically, the Port of HaminaKotka. An analysis of the environmental status is performed mainly as a literature review, because the Finnish ports must comply with Finnish and EU legislation and with the binding international regulations and conventions created by different organizations. The International Maritime Organisation (IMO) has done groundbreaking work in the field of maritime safety and maritime environmental protection. The MARPOL convention has a great impact on decreasing pollution from international shipping and it applies to 99% of the world’s merchant tonnage. Pollution prevention covers: Oil pollution, Chemical pollution, Air pollution and GHG Emissions, Dumping of Wasted and Other Matters, Garbage, Sewage, Port Reception Facilities, Special Areas under MARPOL and Particularly Sensitive Sea Areas. There is also Pollution Prevention for other treaties like anti-fouling systems used on ships, the transfer of alien species by ships’ ballast water and the environmentally sound recycling of ships. There are more than twenty different EU and international regulations that influence ports and port operations in Finland. In addition, there is also national legislation that has an effect on Finnish ports. For the most part, the legislation for ports is common in the EU area, but the biggest and most important difference between the legislation in Finland and other EU countries is due to the Act on Environmental Impact Assessment Procedure. The Act states that the environmental impact assessment procedure shall be applied to projects that may have significant adverse environmental impacts, due to the special features of Finland`s nature and environment. In this Act, the term environmental impact refers to the direct and indirect effects inside and outside Finnish territory of a project or operations on human health, living conditions and amenity; soil, water, air, climate, organisms, interaction between them and biodiversity; community structure, buildings, landscape, townscape and cultural heritage; utilization of natural resources. In Finland, the Environmental Permit requires that ports collect all necessary information concerning environmental effects and make required reports to the Finnish authorities, stakeholders and the public. Commonly, environmental reporting is public and environmental achievements are emphasized in reporting and in media. At the moment, the problem in environmental reporting is that it’s difficult to compare data from different ports. There is enough data concerning the environmental effects and performance, but the manner of reporting and the quality of the data varies between ports. There are differences in the units and codes used, in some cases the information is not sufficient and it can even be rather unreliable. There are also differences regarding the subjects that are emphasized in reporting.

Improving the competitiveness of electrolytic Zinc process by chemical reaction engineering approach

This doctoral thesis describes the development work performed on the leachand purification sections in the electrolytic zinc plant in Kokkola to increase the efficiency in these two stages, and thus the competitiveness of the plant. Since metallic zinc is a typical bulk product, the improvement of the competitiveness of a plant was mostly an issue of decreasing unit costs. The problems in the leaching were low recovery of valuable metals from raw materials, and that the available technology offered complicated and expensive processes to overcome this problem. In the purification, the main problem was consumption of zinc powder - up to four to six times the stoichiometric demand. This reduced the capacity of the plant as this zinc is re-circulated through the electrolysis, which is the absolute bottleneck in a zinc plant. Low selectivity gave low-grade and low-value precipitates for further processing to metallic copper, cadmium, cobalt and nickel. Knowledge of the underlying chemistry was poor and process interruptions causing losses of zinc production were frequent. Studies on leaching comprised the kinetics of ferrite leaching and jarosite precipitation, as well as the stability of jarosite in acidic plant solutions. A breakthrough came with the finding that jarosite could precipitate under conditions where ferrite would leach satisfactorily. Based on this discovery, a one-step process for the treatment of ferrite was developed. In the plant, the new process almost doubled the recovery of zinc from ferrite in the same equipment as the two-step jarosite process was operated in at that time. In a later expansion of the plant, investment savings were substantial compared to other technologies available. In the solution purification, the key finding was that Co, Ni, and Cu formed specific arsenides in the “hot arsenic zinc dust” step. This was utilized for the development of a three-step purification stage based on fluidized bed technology in all three steps, i.e. removal of Cu, Co and Cd. Both precipitation rates and selectivity increased, which strongly decreased the zinc powder consumption through a substantially suppressed hydrogen gas evolution. Better selectivity improved the value of the precipitates: cadmium, which caused environmental problems in the copper smelter, was reduced from 1-3% reported normally down to 0.05 %, and a cobalt cake with 15 % Co was easily produced in laboratory experiments in the cobalt removal. The zinc powder consumption in the plant for a solution containing Cu, Co, Ni and Cd (1000, 25, 30 and 350 mg/l, respectively), was around 1.8 g/l; i.e. only 1.4 times the stoichiometric demand – or, about 60% saving in powder consumption. Two processes for direct leaching of the concentrate under atmospheric conditions were developed, one of which was implemented in the Kokkola zinc plant. Compared to the existing pressure leach technology, savings were obtained mostly in investment. The scientific basis for the most important processes and process improvements is given in the doctoral thesis. This includes mathematical modeling and thermodynamic evaluation of experimental results and hypotheses developed. Five of the processes developed in this research and development program were implemented in the plant and are still operated. Even though these processes were developed with the focus on the plant in Kokkola, they can also be implemented at low cost in most of the zinc plants globally, and have thus a great significance in the development of the electrolytic zinc process in general.

The influence of peeling and type of drying on chemical and sensorial analysis of organic coffee

Organic coffee is characterized by being produced without the use of chemical products and by having a similar or superior quality in comparison to that of coffee produced by traditional methods. The production of organic coffee does not include the use of highly soluble nutrients, which makes consumers concerned with environmental issues and healthy eating habits realize its true value. This paper aims to analyze the influence of harvesting, peeling and drying on the quality of organic coffee, in order to present the best way of producing high quality coffee. Samples of organic coffee were harvested by both conventional and selective ways, and some were peeled. They were then dried on concrete patio and on suspended terraces. The beans were analyzed for potassium leaching, electrical conductivity, titratable acidity, and submitted to coffee cupping-test. The results obtained indicated that the selective harvesting of the peeled or unpeeled cherry coffee dried on concrete terrace is feasible for production of fine coffees. This type of processing effectively influenced the final quality of the organic coffee, thus being an alternative to improve the quality and market value of the product, especially for small producers, cooperatives, and associations of coffee producers.

Chemical composition, fatty acid profile and bioactive compounds of guava seeds (Psidium guajava L.)

This study aimed to characterize the chemical composition, determine the fatty acid profile, and quantify the bioactive compounds present in guava seed powder (Psidium guajava L.). The powder resulted from seeds obtained from guava pulp processing. The agro-industrial seeds from red guava cv. paluma were used, and they were donated by a frozen pulp fruit manufacturer. They contain varying amounts of macronutrients and micronutrients, with a high content of total dietary fiber (63.94 g/100g), protein (11.19 g/100g), iron (13.8 mg/100g), zinc (3.31 mg/100g), and reduced calorie content (182 kcal/100g). Their lipid profile showed a predominance of unsaturated fatty acids (87.06%), especially linoleic acid (n6) and oleic acid (n9). The powder obtained contained significant amounts of bioactive compounds such as ascorbic acid (87.44 mg/100g), total carotenoids (1.25 mg/100 g) and insoluble dietary fiber (63.55 g/100g). With regard to their microbiological quality, the samples were found suitable for consumption. Based on these results, it can be concluded that the powder produced has favorable attributes for industrial use, and that use of these seeds would be a viable alternative to prevent various diseases and malnutrition in our country and to reduce the environmental impact of agricultural waste.

Soil seed bank variation patterns according to environmental factors in a natural grassland

This research aimed to determine the soil seed bank and its relationship with environmental factors that have an influence in the distribution of the vegetation above the ground in an excluded area of natural grassland in the South of Brazil. Most of the 122 identified species in the seed bank were perennials. Data analysis indicated three distinct community groups, according to the size and composition of the soil seed bank in lowlands with permanent wet soils, in lowlands and in other areas. In general, lowlands were characterized by low-fertility soils, high moisture and aluminum contents, being spatially homogeneous habitats and, therefore, more restricted to vegetation heterogeneity than other parts of the relief. Environmental factors most associated with soil seed bank size and composition were relief position and their co-related soil variables such as: soil moisture content, potassium content, organic matter, basic saturation of cation exchange soil capacity, exchangeable basics sum of the soil and clay soil content. According to that, relief position, associated with combined effects of soil chemical properties related to it, determines the observed variation pattern of the soil seed bank, as a reflection of the vegetation above the area.

Diel patterns and tissue-specificity of environmental responses in fish

Humans are profoundly changing aquatic environments through climate change and the release of nutrients and chemicals. To understand the effects of these changes on natural populations, knowledge on individuals’ environmental responses is needed. At the molecular level, the environmental responses are partly mediated by chances in messenger RNA and protein levels. In this thesis I study messenger RNA and protein responses to an assortment of environmental stressors in fish. As daily (diel) rhythms are known to be ubiquitous in different tissues, I particularly focus on diel patterns in the responses. The studied species are the three-spined stickleback (Gasterosteus aculeatus L.) and the Arctic char (Salvelinus alpinus L.), both of which have circumpolar distribution in the Northern hemisphere. In the first two studies, three-spined sticklebacks were exposed to both the non-steroidal anti-inflammatory drug diclofenac and low-oxygen conditions (hypoxia), and their responses measured at separate time points in the liver and gills. The results show how the seemingly unrelated environmental stressors, hypoxia and anti-inflammatory drugs, can have harmful combined effects that differ from the effects of each stressor alone. Moreover, both stressors disturbed natural diel patterns in gene expression. In the third study, I studied the responses of three-spined sticklebacks to two test chemicals: one used in hormonal medicine (17α-ethinyl-oestradiol) and one used as a plasticizer and solvent chemical (di-n-butyl phthalate). The results suggest that the phthalate can affect genes related to spermatogenesis in fish testes, while estrogen-mimicking compounds can lead to numerous disturbances in the endocrine system. In the final study, the temperature-dependence of diel rhythms in messenger RNA levels were evaluated in the liver tissue of the Arctic char, a cold-adapted salmonid. The results show that cold acclimation repressed diel rhythms in gene expression compared to warm-acclimated fish, in which the expression of hundreds of genes was rhythmic, suggesting the circadian clock of the Arctic fish species can be sensitive to temperature. Overall, the results of the thesis indicate that fishes’ responses to abiotic factors interact with their diel rhythms, and more studies on the consequences of these interactions are needed to comprehensively understand human impacts on ecosystems.

Investigation of the composition of linear alkylbenzenes with emphasis on the identification and quantitation of some trace compounds using GS/MS system in both electron impact and chemical ionization modes

Linear alkylbenzenes, LAB, formed by the Alel3 or HF catalyzed alkylation of benzene are common raw materials for surfactant manufacture. Normally they are sulphonated using S03 or oleum to give the corresponding linear alkylbenzene sulphonates In >95 % yield. As concern has grown about the environmental impact of surfactants,' questions have been raised about the trace levels of unreacted raw materials, linear alkylbenzenes and minor impurities present in them. With the advent of modem analytical instruments and techniques, namely GCIMS, the opportunity has arisen to identify the exact nature of these impurities and to determine the actual levels of them present in the commercial linear ,alkylbenzenes. The object of the proposed study was to separate, identify and quantify major and minor components (1-10%) in commercial linear alkylbenzenes. The focus of this study was on the structure elucidation and determination of impurities and on the qualitative determination of them in all analyzed linear alkylbenzene samples. A gas chromatography/mass spectrometry, (GCIMS) study was performed o~ five samples from the same manufacturer (different production dates) and then it was followed by the analyses of ten commercial linear alkylbenzenes from four different suppliers. All the major components, namely linear alkylbenzene isomers, followed the same elution pattern with the 2-phenyl isomer eluting last. The individual isomers were identified by interpretation of their electron impact and chemical ionization mass spectra. The percent isomer distribution was found to be different from sample to sample. Average molecular weights were calculated using two methods, GC and GCIMS, and compared with the results reported on the Certificate of Analyses (C.O.A.) provided by the manufacturers of commercial linear alkylbenzenes. The GC results in most cases agreed with the reported values, whereas GC/MS results were significantly lower, between 0.41 and 3.29 amu. The minor components, impurities such as branched alkylbenzenes and dialkyltetralins eluted according to their molecular weights. Their fragmentation patterns were studied using electron impact ionization mode and their molecular weight ions confirmed by a 'soft ionization technique', chemical ionization. The level of impurities present i~ the analyzed commercial linear alkylbenzenes was expressed as the percent of the total sample weight, as well as, in mg/g. The percent of impurities was observed to vary between 4.5 % and 16.8 % with the highest being in sample "I". Quantitation (mg/g) of impurities such as branched alkylbenzenes and dialkyltetralins was done using cis/trans-l,4,6,7-tetramethyltetralin as an internal standard. Samples were analyzed using .GC/MS system operating under full scan and single ion monitoring data acquisition modes. The latter data acquisition mode, which offers higher sensitivity, was used to analyze all samples under investigation for presence of linear dialkyltetralins. Dialkyltetralins were reported quantitatively, whereas branched alkylbenzenes were reported semi-qualitatively. The GC/MS method that was developed during the course of this study allowed identification of some other trace impurities present in commercial LABs. Compounds such as non-linear dialkyltetralins, dialkylindanes, diphenylalkanes and alkylnaphthalenes were identified but their detailed structure elucidation and the quantitation was beyond the scope of this study. However, further investigation of these compounds will be the subject of a future study.

Chemical Oceanographic Studies of the Coastal Waters of Cochin

The present study is an attempt to understand some of the chemical oceanographic processes of the coastal water and the backwaters of Cochin. The importance of this study lies in the fact that there has been an increasing concern on the environmental degradation of Cochin backwaters with respect to water and sediments due to various anthropogenic activities. The study comprises the results and discussion of the hydro chemical parameters of coastal waters of Cochin during different seasons with statistical analysis. The parameters dealt with are salinity, temperature, pH, dissolved oxygen, nitrite-N, nitrate-N, ammonia-N, Silicate-Si, phosphate-P, chlorophyll ‘a’ and suspended solids, dissolved trace metals and sediment characteristics including sediment metals

Distribution of Benthic In fauna in the Cochin Backwaters In Relation To Environmental Parameters

The study revealed stress and localized impact of industrial waste on the biota, predominance of stress tolerant species and low diversity in the vicinity of the effluent discharge point. These studies on impact of environmental parameters on the distribution of macrobenthos thus indicate the quantum of endurance warranted by the infauna to tide over the wide range of environmental stress. Low diversity and lower number of benthic fauna near discharge site can be attributed to the stress caused by cumulative toxic effects of effluents. The results of the physico-chemical parameters highlight the effects of pollution. The results of the study indicated the changes due to the large-scale movements of the estuarine water under the influence of tide, monsoon and land runoff coupled with its heterogenous nature owing to the effluent discharge from the industries

Semiconductor Oxides Mediated Photocatalytic Removal of Chemical and Bacterial Pollutants from Wastewater

School of Environmental Studies, Cochin University of Science and Technology