Utilização de resíduos de rochas ornamentais na produção de cerâmica branca

The marble and granite waste come from the process of mining of those ornamental rocks for use in the building industry. Brazil is one of the largest producers of blocks or finished products of ornamental rocks, extracting about 5.2 tons / year. The largest national producers are the states of Espírito Santo, Minas Gerais and Bahia which account for 80% of the Brazilian production. However, the waste total amount during processing of these blocks reaches 40% of the total. The use of the waste produced by this industry in white ceramics could be a form of disposition, because these materials, are thrownasa mud directly at decantation ponds, wastelands or in rivers, without any treatment. The present work has as main purpose to study the influence that reject of the ornamental rocks on the physical and mechanical properties of white ceramics. X-Ray characterizations of raw materials by were performed X-Ray fluorescence, X-Ray diffraction, granulometric, thermogravimetric and thermodiferencial analysis, five formulations were made (0, 10, 20, 30, 40% in granite weight) wich were burned at three temperatures: 1100°C, 1150°C and 1200ºC with 60 minutes of sorling time. After sintering, the samples were submitted to different analyser absorption of water, linear retraction, apparent porosity, apparent specific mass, flexival stronght, and scanning were obtained microscopy. Compatible technological properties within the limits demanded for the production of porcelainized stoneware

Eletrofiação e caracterização de membranas biopoliméricas a base de quitosana extraídas dos exoesqueletos de crustáceos

Chitin and chitosan are nontoxic, biodegradable and biocompatible polymers produced by renewable natural sources with applications in diverse areas such as: agriculture, textile, pharmaceutical, cosmetics and biomaterials, such as gels, films and other polymeric membranes. Both have attracted greater interest of scientists and researchers as functional polymeric materials. In this context, the objective of this study was to take advantage of the waste of shrimp (Litopenaeus vannamei and Aristeus antennatus) and crabs (Ucides cordatus) from fairs, beach huts and restaurant in Natal/RN for the extraction of chitin and chitosan for the production of membranes by electrospinning process. The extraction was made through demineralization, deproteinization, deodorization and deacetylation. Morphological analyzes (SEM and XRD), Thermal analysis (TG and DTG), Spectroscopy in the Region of the Infrared with Transformed of Fourier (FTIR) analysis Calorimetry Differential Scanning (DSC) and mechanical tests for traction were performed. In (XRD) the semicrystalline structure of chitosan can be verified while the chitin had higher crystallinity. In the thermal analysis showed a dehydration process followed by decomposition, with similar behavior of carbonized material. Chitosan showed temperature of maximum degradation lower than chitin. In the analysis by Differential Scanning Calorimetry (DSC) the curves were coherent to the thermal events of the chitosan membranes. The results obtained with (DD) for chitosan extracted from Litopenaeus vannamei and Aristeus antennatus shrimp were (80.36 and 71.00%) and Ucides cordatus crabs was 74.65%. It can be observed that, with 70:30 solutions (v/v) (TFA/DCM), 60 and 90% CH3COOH, occurred better facilitate the formation of membranes, while 100:00 (v/v) (TFA/DCM) had formation of agglomerates. In relation to the monofilaments diameters of the chitosan membranes, it was noted that the capillary-collector distance of 10 cm and tensions of 25 and 30 kV contributed to the reduction of the diameters of membranes. It was found that the Young s modulus decreases with increasing concentration of chitosan in the membranes. 90% CH3COOH contributed to the increase in the deformation resulting in more flexible material. The membranes with 5% chitosan 70:30 (v/v) (TFA/DCM) had higher tensile strength

Viabilidade de uso de um fogão solar para cocção de alimentos com parábola refletora fabricada em compósito que utiliza fibras de Carnaúba e resina Ortoftálica

Presents a composite formed by orthophthalic resin and fiber loading of carnauba straw. The fibers were first dried in direct sun exposure and subsequently ground into fodder for the reduction in size. Various formulations of the composite were preliminarily tested by choosing the one presenting the best processability in applying the mold. The composite produced is used for the manufacture of a parabolic surface subsequently coated with mirror segments, flexible plastic, for reflecting the solar rays incident on it. The reflective parable represents the main element of the solar cooker that works with the concentration of sunlight and has dimensions of 1.14 m in diameter and area of 1.0 m². Manufacturing processes and assembly of solar cooker concentration produced are presented. The results of tests for cooking and baking various foods, including rice, pasta, beans, cake, cassava, shrimp, beef, breaded demonstrating the competitiveness of solar cooker studied with other stoves already manufactured and tested in Brazil are presented and in the world. It was also demonstrated the feasibility of the proposed composite for Prototypes manufacture of solar and other structures that do not require great efforts resistance

Estudo da oxidação do metabissulfito de sódio contido no efluente da carcinicultura

The shrimp farming is a process of creation of shrimp that has been growing rapidly in the country, occupying a meaningful space in the Brazilian exporting. In 2003, this activity presented a volume of 60 millions of tons and 220 millions of dollars, being the main generator of employment and income of the primary sector of the northeast economy. However, it is a new activity with c.a. five years in the Rio Grande do Norte State and therefore needs investment in the technological area. Among the wastewaters of this activity, the sulphite solution is being usually applied in the process of fishing, i.e. retrieval of the shrimps from the farming. The aim of this work is to present the oxidation experimental results of the sulphite that may be and to determine what it s the most efficient method, trough laboratory experiments. The measurements were carried out in a mixing reactor inserting air and with hydrogen peroxide addition with and without UV light. The solutions were prepared synthetically with concentrations found in the wastewater of fishing and also collected in locu. The oxidation process using air was monitorated by iodometric analysis for the sulphite and the oxidation using hydrogen peroxide was evaluated with turbidimetric analysis for sulphate, by spectrophotometer. The sulphite was totally oxidized in both processes. The experimental results permit to conclude that the oxidation by hydrogen peroxide is more efficient and allowed to determine the optimum operational conditions in terms of concentration and time of treatment

Dinâmica de Sedimentação de Lodo em Lagoas de Estabilização

Stabilization ponds are an effective sewage treatment alternative for the climatic conditions prevailing in Brazil. In the present work, a primary facultative pond was studied, in the city of Natal, Rio Grande do Norte, Northeast Brazil. The aim of this study was to evaluate the sedimentation dynamics in the facultative pond. The pond was divided in three section or zones along its length starting from the inlet end namely A1, A2 and A3. The research was accomplished in three phases. In the first the mapping of the sludge layer was done, sludge core samples were also collected for analysis for total, fixed and volatile solids and the depth of the sludge layer was determined using a portable echo sounder. In the second solids sedimentation rates were measured using traps placed in the inlet and outlet zones and in the third phase resuspension sludge was evaluate using a tracer. The amount accumulated sludge since the start operation was 13.583 m3. The sedimentation constant averages changed between 0.93 to 2.94 and 3.90 to 5.80 for the depths of 0.5 and 1.0 m respectively. The relationship between volatile and fixed solids (SV/SF) increased along the pond. The removal efficiencies were 52.12%, 36.09%, and 37.50% for BOD, COD and SS, respectively. The sludge accumulation model proposed had a good adjustment with 0.17 m3/hab.year rate. The results presented here demonstrated that the wind had a direct influence on the sedimentation of solids in this pond affecting the efficiency and sludge accumulation

Estratégia de gestão ambiental baseada nos princípios da produção mais limpa : um estudo de caso focado no segmento da carcinicultura

The objective of this scientific article is to introduce the opportunities of implementation of cleaner production (CP) in a shrimp culture farm. The methodology used for this was exploratory research implemented in a production unit located in the Northeast Brazil. The scientific article approaches since generic aspects of the technique about the management to use water, energy and the effluent characterization of this productive activity. It discusses quantitative aspects, environmental questions and chances of P+L during the productive process phases. The results points to input economy in the form of feed, soil correctives, medicines, and energy applied to the process, which range from 4% to 27%, emphasizing the small profit should be viewed as a source of considerable environment return. The authors conclude for the adoption property of this technique in this agribusiness segment, point out to the management importance of the input dosage in the quality of the final effluent, besides the adoption of a physical-chemistry remediation mechanism to the residual of Sodium metabissulphite used in the process of shrimp caught

Concepção de um secador rotatório para secagem do cefalotórax do camarão

The present work has as objective the knowledge of the process of drying of the cephalothorax of shrimp to give support the industry to make possible the use of this byproduct. In this sense, the process conditions in this tray dryer and spouted bed were analyzed. With these results, it was projected and constructs a dryer with specific characteristics for the drying of the cephalothorax. The desorption isotherms were obtained by the dynamic method in the temperatures of 20, 35 and 50º C and in the interval of 10-90% of relative humidity. It was observed that the product in form of powder can be conserved with larger stability for lower relative humidity to 40%. The curves of drying of the dryer of fixed bed were adjusted for the models: single exponential, biparametric exponential and Page. The model biparametric exponential more adequately described all the drying conditions studied. The tests carry out in spouted bed showed high drying rate for the material in the paste form in beds active dynamicly-fluid, provely the necessity of a feeding in shorter intervals of time to increase the thermal efficiency of the process. The projected dryer, be considered the obtained results, it was a rotary dryer with inert bed, feed co-current, discharge in cyclone to take place the separation gas-solid, and feed carry out in intervals of 2 minutes. The optimization of the equipment projected it was accomplished used the complete factorial experimental design 24, this had as independent variables temperature velocity of the air, feed flow rate and encapsulated concentration (albumin), as variables answers the thermal efficiency, the moisture content of obtained powder, total time of test and the efficiency of production of powder in several points of processing. The results showed that the rotary dryer with inert bed can present, also, good results if applied industrially

Evolução da biodegradabilidade da matéria orgânica em um sistema de lagoas de estabilização

Waste stabilization ponds (WSP) have been widely used for sewage treatment in hot climate regions because they are economic and environmentally sustainable. In the present study a WSP complex comprising a primary facultative pond (PFP) followed by two maturation ponds (MP-1 and MP-2) was studied, in the city of Natal-RN. The main objective was to study the bio-degradability of organic matter through the determination of the kinetic constant k throughout the system. The work was carried out in two phases. In the first, the variability in BOD, COD and TOC concentrations and an analysis of the relations between these parameters, in the influent raw sewage, pond effluents and in specific areas inside the ponds was studied. In the second stage, the decay rate for organic matter (k) was determined throughout the system based on BOD tests on the influent sewage, pond effluents and water column samples taken from fixed locations within the ponds, using the mathematical methods of Least Squares and the Thomas equation. Subsequently k was estimated as a function of a hydrodynamic model determined from the dispersion number (d), using empirical methods and a Partial Hydrodynamic Evaluation (PHE), obtained from tracer studies in a section of the primary facultative pond corresponding to 10% of its total length. The concentrations of biodegradable organic matter, measured as BOD and COD, gradually reduced through the series of ponds, giving overall removal efficiencies of 71.95% for BOD and of 52.45% for COD. Determining the values for k, in the influent and effluent samples of the ponds using the mathematical method of Least Squares, gave the following values respectively: primary facultative pond (0,23 day-1 and 0,09 day-1), maturation 1 (0,04 day-1 and 0,03 day-1) and maturation 2 (0,03 day-1 and 0,08 day-1). When using the Thomas method, the values of k in the influents and effluents of the ponds were: primary facultative pond (0,17 day-1 and 0,07 day-1), maturation 1 (0,02 day-1 and 0,01 day-1) and maturation 2 (0,01 day-1 and 0,02 day-1). From the Partial Hydrodynamic Evaluation, in the first section of the facultative pond corresponding to 10% of its total length, it can be concluded from the dispersion number obtained of d = 0.04, that the hydraulic regime is one of dispersed flow with a kinetic constant value of 0.20 day-1

Estudo da circulação hidrodinâmica e da dispersão de óleo na zona costeira entre Macau e Galinhos RN

This paper presents a study on coastal hydrodynamics and the spread of an oil spill in waters off Macau and Galinhos, on the east coast of the state of Rio Grande do Norte in Northeast Brazil. This area has a very marked coastal dynamic owing to the complexity of its geomorphological features, developed in a regime of semidiurnal mesotides involving reefs, spits, estuaries, mangroves, lakes and dunes. The region also plays an important role in the socioeconomic development of the state, given that the production of oil, natural gas, salt and shrimp is concentrated there. The series of oil platforms is interconnected by a pipeline system that carries oil to the local terminal. This pipeline could leak at any moment, causing immense ecological damage. To gauge the risks of an oil leak and resulting contamination of the coastal region, two hydrodynamic scenarios were simulated. The results obtained were used to implement a contaminant transport model with the creation of various oil leak scenarios modeled at different volumes (from small to large) and intensities (sporadic and continuous), at points considered critical for the model (on two platforms and at two pipeline intersections), under different wind (summer and winter) and tidal (high and low at new, full and quarter moon phases) conditions. The use of hydrodynamic circulation computer models as a tool for representing a real project design has been increasingly frequent in recent years, given that they enable the realistic simulation of the hydrodynamic circulation pattern in bodies of water and an analysis of the impacts caused by contaminants released into the water. This study used the computer models contained in SisBAHIA®, in continuous development in the area of Coastal Engineering and Oceanography at COPPE/UFRJ

Variação da qualidade da água do escoamento superficial de duas bacias de drenagem de Natal/RN - Brasil

The urban drainage is one of the powers of environmental sanitation and its scope is the quantitative and qualitative aspects. In decision making of managers and the engineering aspects of design are almost always taken into account only the quantitative aspects. However, the waters of the runoff have the highest concentrations of pollutants at the beginning of precipitation. Thus, if the plot pollution removed, the remaining portion can be used for other purposes. This work has aimed to present the variation of water quality of two drainage basins in the city of Natal / RN-Brazil to support the implementation of drainage to consider the qualitative aspect, and identify potential for the use of water. The basins (M and C) are analyzed closed-type, are in the urban area, are predominantly residential occupation and its waters are used for detention ponds and infiltration. The samples were divided into three phases, the first two direct to final points in a basin and the third in traps distributed over the surface drainage. The parameters had been analyzed were pH, conductivity, dissolved oxygen, Color, Turbidity, COD, Ammonia, nitrite, nitrate, total phosphorus, orthophosphate, Sediments solids, total solids, chloride, sulfate, alkalinity, calcium, magnesium, sodium, potassium, Heavy Metals (Chromium, Cadmium, Lead, Zinc and Copper), Eschichia coli and total coliforms. The parameters studied showed high initial pollution load, events and located in different proportions, except nitrite, heavy metals and biological indicators. The size of the surface drainage and topographic its features influence the quality of water. However, the form of sampling is crucial in the qualitative study in the basin. The samplers developed at work, were generated economic and representative results. The urban rainwater presents organic faecal indicators. The runoff of water from both basins shows no risk of salinity and sodicity for use in irrigation, should be noted the content of chloride in the choice of method of irrigation

Avaliação da eficiência de lagoas de estabilização no tratamento de resíduos esgotados de fossas sépticas

Because of disability in public policy development in mind to attend issues of sanitation in the municipalities, companies known as "clean-blue" appeared proposing to solve a simple collection and management of wastewater produced in single or multifamily residences, commercial, hospitals, etc. In the case of an activity in which there are no worries about the fate of sewage, emerged some doubts about the degree of health and environmental safety in these companies. Traditionally, most of them makes the provision of waste depleted soil or wetland, open, usually located on the outskirts of cities (MENESES, 2001). In turn, the sludge from septic tanks exhausted, provided no technical criteria - in the soil, rivers and as an agricultural fertilizer put in risk the health of the population and environmental quality. This work was entered in the search network 5 of the Notice of the Research Program in Sanitation - PROSAB-5, aimed to study the theme 'Characterization and study of alternative ways of treating sludge from septic tanks in the city of Natal, RN', proposing to evaluate the performance of the use of stabilization ponds as a system to handle waste from septic tanks exhausted. A series of lakes studied belong to one of the largest clean-pit of Natal, consisting of two anaerobic ponds, one facultative and maturation, and a tank disinfection, the wastewater being released in the Potengi River. Samples were collected between the months of October 2007 to October 2008, at six points previously defined and judged as more appropriate to what is proposed study. The analysis results in field and laboratory showed the most significant removal of COD (88.93%), total suspended solids (94.87%), organic nitrogen (66.87%) and thermotolerant coliforms (99.88%). Some results have not reached the expected because the system under study had operating problems that have undermined the efficiency of the reactors

Uso urbano não potável de água de lagoas do sistema de drenagem de Natal

The detention and infiltration ponds of urban drainage system has function to protect the population from undesirable effects of floods. In general these ponds are not completly used and it potential is wasted. As it are disseminated at different places at cities it can reduce costs with water transport and permit water preservation of best quality. Some it utilities includes use in green areas irrigation, industrial among than cooling towers and boiler, soil compaction, cleaning urban road, pisciculture and fire fighting system. The quality these water is influenced by anauthorized sewage in the drainage system. This study was performed in six detention and infiltration ponds at drainage system of Natal, which aim was to verify the non-portable use these ponds on urban environment. As indirect aim would to incentive the water utilization these ponds as a water source to another uses in urban environment. These ponds represents the characteristics of detention and infiltration of Natal city and consequently of Brazil. As the water quality, the ponds presents following characteristics: three has apparently good quality, other showed intermediate condition and two had water polluted. Were performed twenty sample in each ponds and the following parameters assessed: pH, temperature, dissolved oxygen, turbidity, electrical conductivity, coliform thermotolerant, ammonia, organic nitrogen, TKN, nitrate, total phosphorus and alkalinity, bicarbonate, chloride, total hardness, calcium and magnesium hardness, total solids, TSS, TDS, COD and SAR°. To utilization on pisciculture we recommend use in ponds which presents the best quality. Only one pond presented higher pollutants and it not being appropriated for use in cooling tower. The content of solids suspension restricted the water use in all ponds in boilers. As water use in soil compaction, cleaning urban road and fire fighting system the water from these ponds are not appropriated. However, the recommended limits from literature are to domestic sewage, due to this, the parameters are restrictive to diminish the sanitary risk that could be offered with it utilization. The infiltration velocity of water these assessed ponds restrict a moderato use, however the effects are potentiated only in soil less sandy, which not occur in Natal. It is recommend the unrestricted irrigation utilization in ponds with best quality of water, and a restricted irrigation to ponds with worst quality of water. As load of pollutants, it is recommended a complementary treatment in those ponds whit higher load to diminish sanitary risks. In only one pond was found one helminth eggs and due to the convention formula of results, it was found for all ponds less than 1 helminth/liter eggs.

Decaimento bacteriano em lagoas de estabilização no Nordeste brasileiro

Stabilization pond system consisting in more sewage treatment used in Rio Grande do Norte (RN), Brazil, representing about 90% of all systems. Fecal bacteria are removed mainly facultative ponds and in maturation ponds. Many factors influence bacterial decay, such as the levels of pH and DO, temperature, light intensity, HDT and nutrient availability. The bacterial decay rate (Kb) is calculated considering many variables, but the hydraulic regime is a significant influence for microorganisms removal, and the dispersed flow which best characterizes a stabilization pond. However, some authors developed equations for the Kb accordant plug flow and complete mixing. This research study aimed to evaluate the bacterial decay of fecal coliform and Enterococcus sp. in stabilization ponds designed to treat domestic sewage, full-scale, in RN. All systems have assessed pretreatment, a facultative pond (LF) followed by two maturation (LM1 and LM2). The parameters availed were: temperature, pH, DO, BOD5, COD, fecal coliform, Enterococcus sp., Chlorophyll a, total suspended solids, fixed and volatile. In general, there were not significant differences for pH, DO and temperature in the ponds, except for the new systems, since they have low flow and hydraulic loads. The removal of organic matter in the ponds was low, about 70%, and nearly all are overloaded organic and operational problems. The bacterial removals were low, with average 96% for LF for fecal coliform, and 98% for Enterococcus sp.; LM1 were in itself a removal for fecal coliform about 71%, and 81% for Enterococcus sp.; LM2 have efficiency of 69% for fecal coliform, and 68% for Enterococcus sp. The equation proposed by Von Sperling (1999), according to the dispersed flow regime, generated empirical values of Kb more approximate to calculated values of Kb. On average, the calculated Kb to coliforms in the LF was 0.31 d-1, and for both maturation ponds were 0.35 d-1. For Enterococcus sp. the average was 0.40 d-1 for LF, 0.55 d-1 for LM1, and 0.58 d-1 for LM2. These results also showed that the Kb obtained in full-scale systems are smaller than those found in pilot-scale ponds. Moreover, one can say that the equation proposed by Marais (1974), according to the complete-mix regime, overestimates Kb. Actual results of Kb indicated that fecal coliforms are more resistant to adverse conditions present in stabilization ponds than Enterococcus sp., therefore, an indicator of microbiological safety and efficiency. The factors significant interventions in the rate of bacterial decay were concentrations of COD, the organic loading and HDT. The few Kb relationship between pH, DO and temperature were not significant. Finally, we conclude that it s essential to correct operation and maintenance, for not performing these activities is one of the main factors contributing to low rates of bacterial decay.

Remoção de matéria orgânica em sistemas de lagoas de estabilização no Nordeste brasileiro

Stabilization pond is the main technology used for treatment wastewater, in northeast Brazil, due to lower cost of deployment, operation and maintenance compared to other technologies. Most systems of stabilization ponds has been in operation for some time, on average 10 years of operation, receiving high organic loads and do not have good removal efficiencies of the main parameters for which have been designed. Therefore it is necessary to work to quantify the efficiency of current systems. This study evaluated the biodegradability of organic matter in raw sewage, the removal of organic matter in reactors and determination of the kinetic constant removal of organic matter (k), both in reactors and in raw sewage, based on the analysis made in the laboratory and through mathematical methods proposed in the literature, in nine systems stabilization ponds, located in Rio Grande do Norte. In relation the degradation kinetics in stabilization ponds, it was observed that many papers published in the literature were obtained in pilot-scale systems, which often, due to the action of external factors such as wind and temperature, these can t be considered as a reference in the analysis of the kinetic constant K, so the need for more research into systems of scale. This study had three distinct phases and simultaneous, routine monitoring, study of the daily cycle and the determination of kinetic constant of degradation of organic matter (K). The monitoring showed that the removal efficiencies of organic matter on most systems were lower than suggested by the literature, the best efficiencies of around 76% (BOD) and 72% (COD) and the worst of the order of 48% (BOD) and 55% (COD). The calculation of K in raw sewage (Ke) was within the range of variation expected in the literature (0.35 to 0.60 days-1). Already for the results obtained for K in the reactors (Kr), there were well below the values recommended in the literature (0.25 to 0.40 d-1 for complete mix and from 0.13 to 0.17 d-1 for flow dispersed), in line with the overloads that organic systems are subject

Simulação do sistema de esgotamento sanitário de Ponta Negra- Natal: mitigação dos riscos ambientais e estratégia de manutenção preditiva

The simulation of SES-Natal Ponta Negra: mitigation of environmental risks and predictive maintenance strategy was developed in the context of several operational irregularities in the pumping stations and sewage systems in the system Ponta Negra. Thus, the environmental risks and complaints against the company due to overflows of sewage into the public thoroughfare became common. This neighborhood has shown in recent years an increase of resident higher than the initial expectation of growth. In this sense presumed the large population growth and generation of sewers higher than expected, associated to the use of corrective maintenance and misuse of the system may be the main causes of operational failures occurring in the SES. This study aimed at analyzing the hydraulic behavior of SES Ponta Negrathrough numerical simulation of its operation associated to future scenarios of occupation. The SES Ponta Negra has a long lengthof collection networks and 6 pumping stations interconnected, being EE 1, 2, 4 coastal way, and beach Shopping interconnected EE3 to receives all sewers pumped from the rest pumping station and pumped to the sewage treatment station of neighborhood which consists of a facultative pond followed by three maturation ponds with disposal of treated effluent into infiltration ditches. Oncethey are connected with each other, the study was conducted considering the days and times of higher inflow for all lifts. Furthermore, with the aim of measuring the gatherer network failures were conducted data survey of on the networks. Thephysical and operational survey data was conducted between January/2011 and janeiro/2012. The simulation of the SES was developed with the aim ofdemonstrating its functioning, eithercurrently and in the coming years, based in population estimates and sewage flow. The collected data represents the current framework of the pumping stations of the SES Ponta Negra and served as input to the model developed in MS Excel ® spreadsheet which allowed simulating the behavior of SES in future scenarios. The results of this study show thatBeach Shopping Pumping Station is actually undersized and presents serious functioning problemsthatmay compromise the environmental quality of surrounding area. The other pumping stations of the system will reach itsmaximum capacity between 2013 and 2015, although the EE1 and EE3 demonstrateoperation capacity, even precariously, until 2017. Moreover, it was observed that the misuse of the network system, due to the input of both garbage and stormwater, are major factors of failures that occur in the SES. Finally, it was found that the corrective maintenance appliance, rather than predictive,has proven to beinefficient because of the serious failuresin the system, causing damage to the environment and health risks to users