Enzymatic activity measured by microcalorimetry in soil amended with organic residues

Enzymatic activity is an important property for soil quality evaluation. Two sequences of experiments were carried out in order to evaluate the enzymatic activity in a soil (Rhodic Eutrudox) amended with cattle manure, earthworm casts, or sewage sludges from the municipalities of Barueri and Franca. The activity of commercial enzymes was measured by microcalorimetry in the same soil samples after sterilization. In the first experiment, the enzyme activities of cellulase, protease, and urease were determined in the soil samples during a three month period. In the second sequence of experiments, the thermal effect of the commercial enzymes cellulase, protease, and urease on sterilized soil samples under the same tretaments was monitored for a period of 46 days. The experimental design was randomized and arranged as factorial scheme in five treatments x seven samplings with five replications. The treatment effects were statistically evaluated by one-way analysis of variance. Tukey´s test was used to compare means at p < 0.05. The presence of different sources of organic residues increased the enzymatic activity in the sampling period. Cattle manure induced the highest enzymatic activity, followed by municipal sewage sludge, whereas earthworm casts induced the lowest activity, but differed from control treatment. The thermal effect on the enzyme activity of commercial cellulase, protease, and urease showed a variety of time peaks. These values probably oscillated due to soil physical-chemical factors affecting the enzyme activity on the residues.

Industrial and urban organic wastes increase soil microbial activity and biomass

Microbial processes have been used as indicators of soil quality, due to the high sensitivity to small changes in management to evaluate, e.g., the impact of applying organic residues to the soil. In an experiment in a completely randomized factorial design 6 x 13 + 4, (pot without soil and residue or absolute control) the effect of following organic wastes was evaluated: pulp mill sludge, petrochemical complex sludge, municipal sewage sludge, dairy factory sewage sludge, waste from pulp industry and control (soil without organic waste) after 2, 4, 6, 12, 14, 20, 28, 36, 44, 60, 74, 86, and 98 days of incubation on some soil microbial properties, with four replications. The soil microbial activity was highly sensitive to the carbon/nitrogen ratio of the organic wastes. The amount of mineralized carbon was proportional to the quantity of soil-applied carbon. The average carbon dioxide emanating from the soil with pulp mill sludge, corresponding to soil basal respiration, was 0.141 mg C-CO2 100 g-1 soil h-1. This value is 6.4 times higher than in the control, resulting in a significant increase in the metabolic quotient from 0.005 in the control to 0.025 mg C-CO2 g-1 Cmic h-1 in the soil with pulp mill sludge. The metabolic quotient in the other treatments did not differ from the control (p < 0.01), demonstrating that these organic wastes cause no disturbance in the microbial community.

Influence of digestion methods on the recovery of Iron, Zinc, Nickel, Chromium, Cadmium and Lead contents in 11 organic residues

There are currently many devices and techniques to quantify trace elements (TEs) in various matrices, but their efficacy is dependent on the digestion methods (DMs) employed in the opening of such matrices which, although "organic", present inorganic components which are difficult to solubilize. This study was carried out to evaluate the recovery of Fe, Zn, Cr, Ni, Cd and Pb contents in samples of composts and cattle, horse, chicken, quail, and swine manures, as well as in sewage sludges and peat. The DMs employed were acid digestion in microwaves with HNO3 (EPA 3051A); nitric-perchloric digestion with HNO3 + HClO4 in a digestion block (NP); dry ashing in a muffle furnace and solubilization of residual ash in nitric acid (MDA); digestion by using aqua regia solution (HCl:HNO3) in the digestion block (AR); and acid digestion with HCl and HNO3 + H2O2 (EPA 3050). The dry ashing method led to the greatest recovery of Cd in organic residues, but the EPA 3050 protocol can be an alternative method for the same purpose. The dry ashing should not be employed to determine the concentration of Cr, Fe, Ni, Pb and Zn in the residues. Higher Cr and Fe contents are recovered when NP and EPA 3050 are employed in the opening of organic matrices. For most of the residues analyzed, AR is the most effective method for recovering Ni. Microwave-assisted digestion methods (EPA3051 and 3050) led to the highest recovery of Pb. The choice of the DM that provides maximum recovery of Zn depends on the organic residue and trace element analyzed.

Soluble carbon in oxisol under the effect of organic residue rates

The application of organic residues to the soil can increase soluble organic carbon (SOC) and affect the pH and electrolytic conductivity (EC) of the soil. However, the magnitude of these changes depends on the type of residue and the applied dose. This study aimed to evaluate the effect of increasing C rates contained in organic residue on the pH, EC, water-extractable total carbon (WETC), water-extractable organic carbon (WEOC), and water-extractable inorganic carbon (WEIC) in soil treated with manure (chicken, swine, and quail), sawdust, coffee husk, and sewage sludge. The levels of total C (TC- KH2PO4), organic carbon (OC- KH2PO4), and inorganic C (IC- KH2PO4) extractable by a 0.1 mol L-1 KH2PO4 solution were also quantified in soil under the effect of increasing rates of chicken and quail manures. The following rates of organic residue C were applied to a dystrophic Red Latosol (Oxisol) sample: 0, 2,000, 5,000, 10,000, and 20,000 mg kg-1. The addition of organic residues to the soil increased pH, except in the case of sewage sludge, which acidified the soil. The acidity correction potential of chicken and quail manure was highest, dependent on the manure rate applied; regardless of the dose used, sawdust barely alters the soil pH. At all tested rates, the EC of the soil treated with swine manure, coffee husk, and sawdust remained below 2.0 dS m-1, which is a critical level for salinity-sensitive crops. However, the application of chicken or quail manure and sewage sludge at certain rates increased the EC to values above this threshold level. Highest levels of WETC, WEOC, and WEIC were obtained when chicken and quail manure and coffee husk were applied to the Oxisol. The quantities of SOC extracted by KH2PO4 were higher than the quantities extracted by water, demonstrating the ability of soil to adsorb C into its colloids.

BIOCHAR: PYROGENIC CARBON FOR AGRICULTURAL USE - A CRITICAL REVIEW

Biochar (carbonized biomass for agricultural use) has been used worldwide as soil amendment and is a technology of particular interest for Brazil, since its "inspiration" is from the historical Terra Preta de Índios(Amazon Dark Earth), and also because Brazil is the world's largest charcoal producer, generating enormous residue quantities in form of fine charcoal and due to the availability of different residual biomasses, mainly from agroindustry (e.g., sugar-cane bagasse; wood and paper-mill wastes; residues from biofuel industries; sewage sludge etc), that can be used for biochar production, making Brazil a key actor in the international scenario in terms of biochar research and utilization). In the last decade, numerous studies on biochar have been carried out and now a vast literature, and excellent reviews, are available. The objective of this paper is therefore to deliver a critical review with some highlights on biochar research, rather than an exhaustive bibliographic review. To this end, some key points considered critical and relevant were selected and the pertinent literature "condensed", with a view to guide future research, rather than analyze trends of the past.

RECOVERY OF AN OXISOL DEGRADED BY THE CONSTRUCTION OF A HYDROELECTRIC POWER PLANT

ABSTRACT The removal of thick layers of soil under native scrubland (Cerrado) on the right bank of the Paraná River in Selvíria (State of Mato Grosso do Sul, Brazil) for construction of the Ilha Solteira Hydroelectric Power Plant caused environmental damage, affecting the revegetation process of the stripped soil. Over the years, various kinds of land use and management systems have been tried, and the aim of this study was to assess the effects of these attempts to restore the structural quality of the soil. The experiment was conducted considering five treatments and thirty replications. The following treatments were applied: stripped soil without anthropic intervention and total absence of plant cover; stripped soil treated with sewage sludge and planted to eucalyptus and grass a year ago; stripped soil developing natural secondary vegetation (capoeira) since 1969; pastureland since 1978, replacing the native vegetation; and soil under native vegetation (Cerrado). In the 0.00-0.20 m layer, the soil was chemically characterized for each experimental treatment. A 30-point sampling grid was used to assess soil porosity and bulk density, and to assess aggregate stability in terms of mean weight diameter (MWD) and geometric mean diameter (GMD). Aggregate stability was also determined using simulated rainfall. The results show that using sewage sludge incorporated with a rotary hoe improved the chemical fertility of the soil and produced more uniform soil pore size distribution. Leaving the land to develop secondary vegetation or turning it over to pastureland produced an intermediate level of structural soil quality, and these two treatments produced similar results. Stripped soil without anthropic intervention was of the lowest quality, with the lowest values for cation exchange capacity (CEC) and macroporosity, as well as the highest values of soil bulk density and percentage of aggregates with diameter size <0.50 mm, corroborated by its lower organic matter content. However, the percentage of larger aggregates was higher in the native vegetation treatment, which boosted MWD and GMD values. Therefore, assessment of some land use and management systems show that even decades after their implementation to mitigate the degenerative effects resulting from the installation of the Hydroelectric Plant, more efficient approaches are still required to recover the structural quality of the soil.

Efficiency of five biosolids to supply nitrogen and phosphorus to ryegrass

Biosolids have been considered satisfactory to supply crops and plant nutrients. The ideal biosolids application rate should result in high crop yields and nutrient uptake, and leave low concentrations of nutrients in soils to avoid environmental problems. The objective of this study was to estimate the capacity of five biosolids to supply N and P to ryegrass (Lolium perenne) after a single application of either fertilizers or biosolids to a Spodosol and an Oxisol. Results showed that 6% - 36% of N and 3% - 7% of P applied as biosolids were recovered in plants grown on the Spodosol, while the range on the Oxisol was 26%-75% for N and 1.2%-3.7% for phosphorus. Biosolids' efficiency on supplying N and P to plants was similar to fertilizer on the Spodosol, but on the Oxisol it refrained to 65%-67% fertilizer's efficiency. After a single application of biosolids followed by six consecutive harvests, 25%-94% of the N and 93%-99% of the P were not used by plants and remain in the soils.

Libro de Actas II Congreso Español de Gestión Integral de Deyecciones Ganaderas

Postprint (published version)

Dynamic Modelling of Material Flows and Sustainable Resource Use: Case Studies in Regional Metabolism and Space Life Support Systems

Sustainable resource use is one of the most important environmental issues of our times. It is closely related to discussions on the 'peaking' of various natural resources serving as energy sources, agricultural nutrients, or metals indispensable in high-technology applications. Although the peaking theory remains controversial, it is commonly recognized that a more sustainable use of resources would alleviate negative environmental impacts related to resource use. In this thesis, sustainable resource use is analysed from a practical standpoint, through several different case studies. Four of these case studies relate to resource metabolism in the Canton of Geneva in Switzerland: the aim was to model the evolution of chosen resource stocks and flows in the coming decades. The studied resources were copper (a bulk metal), phosphorus (a vital agricultural nutrient), and wood (a renewable resource). In addition, the case of lithium (a critical metal) was analysed briefly in a qualitative manner and in an electric mobility perspective. In addition to the Geneva case studies, this thesis includes a case study on the sustainability of space life support systems. Space life support systems are systems whose aim is to provide the crew of a spacecraft with the necessary metabolic consumables over the course of a mission. Sustainability was again analysed from a resource use perspective. In this case study, the functioning of two different types of life support systems, ARES and BIORAT, were evaluated and compared; these systems represent, respectively, physico-chemical and biological life support systems. Space life support systems could in fact be used as a kind of 'laboratory of sustainability' given that they represent closed and relatively simple systems compared to complex and open terrestrial systems such as the Canton of Geneva. The chosen analysis method used in the Geneva case studies was dynamic material flow analysis: dynamic material flow models were constructed for the resources copper, phosphorus, and wood. Besides a baseline scenario, various alternative scenarios (notably involving increased recycling) were also examined. In the case of space life support systems, the methodology of material flow analysis was also employed, but as the data available on the dynamic behaviour of the systems was insufficient, only static simulations could be performed. The results of the case studies in the Canton of Geneva show the following: were resource use to follow population growth, resource consumption would be multiplied by nearly 1.2 by 2030 and by 1.5 by 2080. A complete transition to electric mobility would be expected to only slightly (+5%) increase the copper consumption per capita while the lithium demand in cars would increase 350 fold. For example, phosphorus imports could be decreased by recycling sewage sludge or human urine; however, the health and environmental impacts of these options have yet to be studied. Increasing the wood production in the Canton would not significantly decrease the dependence on wood imports as the Canton's production represents only 5% of total consumption. In the comparison of space life support systems ARES and BIORAT, BIORAT outperforms ARES in resource use but not in energy use. However, as the systems are dimensioned very differently, it remains questionable whether they can be compared outright. In conclusion, the use of dynamic material flow analysis can provide useful information for policy makers and strategic decision-making; however, uncertainty in reference data greatly influences the precision of the results. Space life support systems constitute an extreme case of resource-using systems; nevertheless, it is not clear how their example could be of immediate use to terrestrial systems.

Aqueous photocatalytic oxidation of steroid estrogens

Concerns have increased regarding the detection of endocrine-disrupting compounds in the effluents of sewage treatment plants (STPs). These compounds are able to disrupt normal function of the endocrine system of living organisms even at trace concentrations. Natural and synthetic steroid estrogens (SEs) are believed to be responsible for the majority of the endocrine-disrupting effects. Municipal sewage, the main source of SEs in the environment, is a complex mixture of a wide range of pollutants at concentrations much higher than those of SEs. Low concentrations of SEs in the presence of copollutants thus make their removal problematic. The main objectives of the present work were to study the potential of photocatalytic oxidation (PCO) to effectively treat SE-containing aqueous solutions and to identify the optimum conditions for such treatment. The results showed that SEs can be effectively degraded photocatalytically. Due to the adsorption properties of SEs on the TiO2 photocatalyst surface alkaline medium was found to be beneficial for SE oxidation despite the presence of co-pollutants in concentrations characteristic for the sanitary fraction of municipal sewage. The potential of PCO to selectively oxidise SEs was examined in the presence of copollutants of the sanitary fraction of sewage - urea, saccharose and human urine. The impact of ethanol, often used as a solvent in the preparation of SE stock solutions, was also studied and the results indicated the need to use organic solvent-free solutions for the study of SE behaviour. Photocatalytic oxidation of SEs appeared to be indifferent towards the presence of urea in concentrations commonly found in domestic sewage. The effect of other co-pollutants under consideration was far weaker than could be expected from their concentrations, which are from one hundred to a few thousands times higher than those of the SEs. Although higher concentrations can dramatically slow down the PCO of SEs, realistic concentrations of co-pollutants characteristic for the sanitary fraction of domestic sewage allowed selective removal of SEs. This indicates the potential of PCO to be a selective oxidation method for SE removal from the separate sanitary fraction of municipal sewage.

Yhdyskuntalietteen ja biopolttoaineiden käsittelyketjujen ja polton teknistaloudellinen tarkastelu

Työn tavoitteena on kartoittaa yhdyskuntalietteen ja kierrätys- sekä biopolttoaineiden käsittelyä ja polttoa lietteenpolttolaitoksen tarpeita ajatellen. Lietteen käsittelyketjun ja kierrätys- sekä biopolttoaineketjujen tekninen tarkastelu on siis työn keskeinen tavoite. Lisäksi lasketaan polttolaitoksen suurimpia mahdollisia investointikustannuksia eri polttoainevaihtoehdoilla. Työssä tehdään muun ohella case-tarkastelua Kaakkois- Suomen alueeseen liittyen. Tavoitteena on muodostaa tarkoitukseen soveltuva polttoaineratkaisu kullekin tapauk-selle. Työn alkuosassa tutustutaan yleisesti lietteeseen sekä polttoaineen että jätteen roolissa. Tarkastelu sisältää tietoja lietteen ominaisuuksista sekä lietteenkäsittelyssä olennaisista lainsäädännöllisistä seikoista. Samoin katsastetaan hieman lietteen esikäsittelyä, mekaanista vedenerotusta, termistä kuivausta ja polttoa tarkastellaan yleisessä valossa. Lisäksi alkuosassa keskitytään eri bio- jakierrätyspolttoainevaihtoehtoihin tarkastelemalla niiden yleisyyttä polttoaineena sekä esittelemällä niiden käsittelyketjuja. Työn loppupuoliskolla kiinnitetään huomiota case tapausten avulla polttolaitoksesta saataviin tuottoihin sekä millaisen liikkumavaran eri polttoainevaihtoehdot investointien osalta sallivat. Case-tapauksissa pohditaan Kymenlaakson ja Etelä-Karjalan paikallisia lietteen-polttomahdollisuuksia yhdistettynä kierrätys- tai biopolttoaineisiin. Mekaanisesti kuivattua lietettä käsitellään kyseisissä tapauksissa vuosittain 6000 t ja 15 000 t. Lietteen polton tuottama sähkö- ja lämpöteho näyttävät riippuvan voimakkaasti lietteen kuiva-ainepitoisuudesta, eivät niinkään lietteen muista ominaisuuksista. Lisäksi joko bio- tai kierrätyspolttoaineella saadaan sähkön- ja lämmöntuotantoa nostettua huomattavasti.

Yhdyskuntalietteen käsittely ennen termistä kuivausta ja polttoa

Työn tavoitteena on kartoittaa yhdyskuntalietteen käsittelyä lietteenpolttolaitoksen tarpeita ajatellen. Lietteen käsittelytekniikoiden ja kuljetusvaihtoehtojen selvittäminen on siis työn keskeinen tavoite. Lisäksi otetaan selvää näiden tekijöiden kustannusrakenteesta. Yhdyskuntalietteen ominaisuuksien sekä käsittelyyn liittyvien ongelmakohtien valottaminen kuuluu samoin työn tavoitteisiin. Työssä tehdään muun ohella case-tarkastelua Kaakkois-Suomen alueeseen liittyen. Tavoitteena on muodostaa tarkoitukseen soveltuva lietteenkäsittelymalli kullekin tapaukselle. Työn alkuosassa tutustutaan yleisesti lietteeseen sekä polttoaineen että jätteen roolissa. Tarkastelu sisältää tietoja lietteen ominaisuuksista ja muodostuvista määristä sekä lietteenkäsittelyssä olennaisista lainsäädännöllisistä seikoista. Samoin katsastetaan hieman jäteve¬denpuhdistusprosessiin sekä näin ollen lietteen syntyyn. Lietteen esikäsittelyä, mekaanista vedenerotusta, termistä kuivausta ja polttoa tarkastellaan yleisessä valossa. Mekaanisen vedenerotuksen osalta myös eritellään ja vertaillaan laitteita. Etenkin linko, mutta myös suotonauhapuristin osoittautuivat erityisen sopiviksi kunnallisen lietteen käsittelyyn. Työn loppupuoliskolla kiinnitetään huomiota lietteen varastointiin sekä syöttö-ja purkumenetelmiin, lyhyen etäisyyden siirtoon ja pidemmän matkan kuljetukseen. Case-tapauksissa pohditaan Kymenlaakson ja Etelä-Karjalan paikallisia lietteenkäsittelymahdollisuuksia. Mekaanisesti kuivattua lietettä käsitellään kyseisissätapauksissa vuosittain 6000 t ja 15 000 t. Lietteen polton tuottama sähkö- ja lämpöteho näyttävät riippuvan voimakkaasti lietteen kuiva-ainepitoisuudesta, eivät niinkään lietteen muista ominaisuuksista. Lietteenkäsittelykustannukset tiivistetystä lietteestä termiseen kuivaukseen soveltuvaksi polttoaineeksi vaihtelevat10-20 \ lietetonnia kohden, riippuen käsittelyvaiheiden määrästä. Kustannuksia syntyy eniten mekaanisesta vedenerotuksesta ja varastoinnista.

Kaatopaikkakaasun hyötykäyttömahdollisuudet Anjalankosken Ekoparkissa

Kaatopaikalle sijoitetut biohajoavat orgaaniset jätteet muodostavat jätetäytön hapettomissa olosuhteissa kaatopaikkakaasua, joka koostuu pääasiassa metaanista ja hiilidioksidista. Kaatopaikkakaasun sisältämän metaanin takia, kaasusisältää merkittävästi energiaa, joka on hyödynnettävissä eri tavoin. Tämän diplomityön tavoitteena oli tarkastella vaihtoehtoja Anjalankosken Keltakankaan kaatopaikoilla muodostuvan kaatopaikkakaasun hyödyntämiseksi. Tarkastellut vaihtoehdot tarjoavat ympäristöllisten hyötyjen lisäksi liiketoiminnallista hyötyä Ekoparkissa toimiville yrityksille. Tutkimuksessa tehdyt laskelmatosoittivat, että työssä tarkastellut kaatopaikkakaasun hyötykäyttövaihtoehdot ovat sekä taloudellisesti että kaasun riittävyyden kannalta hyödynnettävissä. Esimerkiksi kaatopaikkakaasun hyödyntämisellä kaukolämmön tuotannossa voidaan kattaa noin kolmannes Anjalankosken vuotuisesta kaukolämmön tarpeesta. Kaatopaikkakaasun lietteen kuivauskapasiteetti kattaa Pohjois-Kymenlaaksossa muodostuvan jätevesilietteen käsittelytarpeen. Biopolttoaineen kuivauskapasiteetti on riittävä olemassa oleviin valmistuslaitosten tuotantokapasiteetteihin verrattuna. Myös perinteisillä sähkön- ja lämmöntuotantotekniikoilla voidaan kattaa Ekoparkin oma sähkön- ja lämmöntarve. Kaatopaikkavesien haihdutus ei tulosten perusteella ole sekä taloudellisesti että kaasun riittävyyden kannalta hyödynnettävissä. Tuhkan vitrifioinnissa haasteen muodostaa investointikustannuksen suuruus. Anjalankosken Ekoparkin yritykset voivat hyödyntää työn tuloksia uuden liiketoiminnan kehittämiseen. Lisäksi tuloksia voidaan hyödyntää soveltaen eri kokoluokan kaatopaikkojen kaatopaikkakaasujen hyötykäyttöä suunniteltaessa.

Revegetació de talussos d'una explotació carbonífera mitjançant materials de rebuig

En aquest treball s'avalua la rehabilitació dels talussos d'una explotació minera carbonífera utilitzant materials de rebuig de la pròpia explotació i provinents d'activitats ramaderes (purins de porc) o urbanes (llots de depuradora), en un ambient àrid del Baix Segre. Les variables analitzades foren el tipus i recobriment vegetals, la penetromia i la salinitat del substrat, i la salinitat, els nitrats i els sediments dels efluents. Els resultats indiquen que és possible rehabilitar els runams en aquests medis, assolint recobriments vegetals fins al 50 % sense que se'n derivin efectes ambientals negatius importants. Taxes altes puntuals d'erosió poden controlar-se amb un disseny adient dels talussos. L'aplicació superficial de purí no té efectes antiencrostants. La moderada salinitat dels substrats condiciona l'establiment de vegetació halòfila.

Assessing changes in Cd phytoavailability to tomato in amended calcareous soils.

A plot study was conducted to assess changes in Cd phytoavailability to a tomato cultivar in an agricultural soil in Southeastern Spain amended in two different ways (A and B), under controlled conditions. The experimental soil corresponded to a fine-loamy carbonatic thermic Calcidic Haploxeroll (Soil Survey Staff, 1998). A) Soil was amended with a single application of sewage sludge from a municipal source that had a total Cd concentration of 0.5 mg kg-1 at a rate that represented a final average concentration in the mixture of soil and sludge of less than 50 µg Cd kg-1. B) The amendment consisted of the addition of a mineral fertiliser with the same amount of NPK as in the sewage sludge application. The final levels of Cd were supposed to be negligible. A plot series without amendments was also performed (C). DTPA plus triethanolamine, and ammonium acetate extractable fractions in soils were analysed for all the plots. The time-dependent Cd accumulation in different parts of the tomato plants was studied by means of a Cd salt treatment. For each block (A, B, and C) four levels of Cd (0, 3, 30, 100 mg kg-1) were added as CdCl2. There was a significant increase in plant Cd after the initial cropping. Tomato stems, leaves and fruits were analysed separately for Cd determination. Differential Cd distribution and accumulation in tomato parts was detected.