Acidification and solar drying of manure-based digestate to produce improved fertilizing products.

The increase in energy and fertilizer consumption makes it necessary to develop sustainable alternatives for agriculture. Anaerobic digestion and digestates appeared to be suitable options. However, untreated digestates still have high water content and can increase greenhouse gas emissions during storage and land application. In this study, manure-derived digestate and solid fraction of digestate after separation were treated with a novel solar drying technology to reduce their water content, combined with acidification to reduce the gaseous emissions. The acidified digestate and acidified solid fraction of digestate recovered more nitrogen and ammonia nitrogen than their respective non-acidified products (1.5-1.3 times for TN; 14 times for TAN). Ammonia and methane emissions were reduced up to 94% and 72% respectively, compared to the non-acidified ones, while N2O increased more than 3 times. Dried digestate and dried acidified digestate can be labeled as NPK organic fertilizer regarding the European regulation, and the dried solid fraction and the improved dried acidified solid fraction can be labeled as N or P organic fertilizer. Moreover, plant tests showed that N concentrations in fresh lettuce leaves were within the EU limit with all products in all the cases. However, zinc concentration appeared to be a limitation in some of the products as their concentration exceeded the European legal limits.

Techno-economic assessment at full scale of a biogas refinery plant receiving nitrogen rich feedstock and producing renewable energy and biobased fertilisers.

Anaerobic digestion of nitrogen (N) rich substrates might be hindered when ammonia (NH3) formation reaches toxic levels for methanogenic microorganisms. One possible strategy to avoid inhibiting conditions is the removal of NH3 from digestate by stripping and scrubbing technology and by recirculating N depleted digestate back to the digester. This study aimed to i) monitor the performance (mass and energy balances) of a full scale digestate processing cascade that includes an innovative vacuum side stream NH3stripping and scrubbing system, ii) assess the production cost of ammonium sulphate (AS) solution and iii) evaluate its fertiliser quality. The use of gypsum to recover NH3 in the scrubbing unit, instead of the more common sulphuric acid, results in the generation of AS and a fertilising liming substrate. Mass and nutrient balances indicated that 57% and 7.5% of ammonium N contained in digestate was recovered in the form of a 22% AS and liming substrate, respectively. The energy balance showed that about 3.8 kWhel and 59 kWhth were necessary to recover 1 kg of N in the form of AS. Furthermore, the production cost of AS, including both capital and operational costs, resulted to be 5.8 € t-1 of digestate processed. According to the fertiliser quality assessment, this technology allows for the recovery of NH3in the form of salt solutions that can be utilised as a substitute for synthetic mineral nitrogen fertilisers.

Metal sorption by biochars: A trade-off between phosphate and carbonate concentration as governed by pyrolysis conditions.

Three feedstocks, pine wood, grass and cow manure, were pyrolyzed under various conditions and tested on their ability to sorb metals in aquatic systems. The feedstocks were pyrolyzed at 2 different temperatures (350 °C and 550 °C) and 2 different residence times (10 and 60 min) and resulting biochars were assessed on their capability to immobilize Pb, Cu, Cd and Zn. Manure-based chars, and to a lesser extent grass-based chars, featured high concentrations of phosphates and carbonates. These anions play an important role in metal sorption because they form insoluble complexes with the metals. Washing reduced the concentration of these anions, leading to a reduced sorption of metals by the biochar. The carbonate concentration on the biochars' surface increased at higher reactor temperature and longer residence times. The opposite trend was observed for the phosphate concentration and the cation exchange capacity. Accordingly, the optimal temperature-residence time combination for sorption was a trade-off between these properties. Biochar produced from cow manure and pyrolyzed at 550 °C for 10 min showed the best sorption for all metals considered.

Periodontal screening and referral behaviour of general dental practitioners in Flanders.

OBJECTIVES: The objective of this study was to investigate the screening and referral behaviour of Flemish dentists concerning periodontitis and more specific, the use of the Dutch Periodontal Screening Index (DPSI). MATERIALS AND METHODS: An online questionnaire was electronically distributed through the different professional dental societies. It consisted of two parts: the first aimed at describing the profile of the dentist. The second part inquired the screening method, when this was applied, periodontal risk factors and referral behaviour. RESULTS: One thousand fifty dentists attended to the questionnaire. One hundred fifty-nine questionnaires were excluded since they did not match the target audience. Sixty-four percent of Flemish dentists used DPSI as a periodontal screening method, 28% screened based on probing pocket depth, 4% used solely radiographs and 4% had no screening method at all. The usage of DPSI is influenced by the year of graduation: the longer the dentists were graduated, the less they used DPSI. No influence of sex, education centre and location was found. Referral behaviour is influenced by different patient- and dentist-related factors. CONCLUSIONS: Regarding the screening behaviour, there seems a consensus among Flemish dentists that a periodontal probe should be used. For referral, there is no consensus about if and when to refer to a specialist. CLINICAL RELEVANCE: It is encouraging that 92% of the Flemish general dental practitioners use a probe when screening for periodontitis. However, DPSI is mainly used by younger dentists. An effort should be made to encourage all dentists to use this, so that in every patient, periodontitis can be detected timely, securing the best treatment outcome.

Upflow anaerobic sludge blanket and aerated constructed wetlands for swine wastewater treatment: a pilot study.

Swine wastewater management is often affected by two main issues: a too high volume for optimal reuse as a fertilizer and a too high strength for an economically sustainable treatment by classical solutions. Hence, an innovative scheme has been tested to treat swine wastewater, combining a low cost anaerobic reactor, upflow anaerobic sludge blanket (UASB), with intensified constructed wetlands (aerated CWs) in a pilot scale experimental study. The swine wastewater described in this paper is produced by a swine production facility situated in North Italy. The scheme of the pilot plant consisted of: (i) canvas-based thickener; (ii) UASB; (iii) two intensified aerated vertical subsurface flow CWs in series; (iv) a horizontal flow subsurface CW. The influent wastewater quality has been defined for total suspended solids (TSS 25,025 ± 9,323 mg/l), organic carbon (chemical oxygen demand (COD) 29,350 ± 16,983 mg/l), total reduced nitrogen and ammonium (total Kjeldahl nitrogen (TKN) 1,783 ± 498 mg/l and N-NH4+ 735 ± 251 mg/l) and total phosphorus (1,285 ± 270 mg/l), with nitrates almost absent. The overall system has shown excellent performances in terms of TSS, COD, N-NH4+ and TKN removal efficiencies (99.9%, 99.6%, 99.5%, and 99.0%, respectively). Denitrification (N-NO3- effluent concentration equal to 614 ± 268 mg/l) did not meet the Italian quality standards for discharging in water bodies, mainly because the organic carbon was almost completely removed in the intensified CW beds.

Enhanced phytoextraction of uranium and selected heavy metals by Indian mustard and ryegrass using biodegradable soil amendments.

The applicability of biodegradable amendments in phytoremediation to increase the uptake of uranium (U), cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb) and zinc (Zn) by Indian mustard (Brassica juncea) and ryegrass (Lolium perenne) was tested in a greenhouse experiment. Plants were cultivated during one month on two soils with naturally or industrially increased contaminant levels of U. Treatments with citric acid, NH4-citrate/citric acid, oxalic acid, S,S-ethylenediamine disuccinic acid (EDDS) or nitrilotriacetic acid (NTA) at a rate of 5 mmol kg(-1) dry soil caused increases in soil solution concentrations that were up to 18 times higher for U and up to 1570 times higher for other heavy metals, compared to the controls. Shoot concentrations increased to a much smaller extent. With EDDS, 19-, 34-, and 37-fold increases were achieved in shoots of Indian mustard for U, Pb and Cu, respectively. The increases in plant uptake of Cd, Cr and Zn were limited to a factor of four at most. Ryegrass generally extracted less U and metals than Indian mustard. Despite a marked increase of U and metal concentrations in shoots after addition of amendments, the estimated time required to obtain an acceptable reduction in soil contaminant concentrations was impractically long. Only for Cu and Zn in one of the studied soils, could the Flemish standards for clean soil theoretically be attained in less than 100 years.

Presence and mobility of arsenic in estuarine wetland soils of the Scheldt estuary (Belgium).

We aimed to assess the presence and availability of arsenic (As) in intertidal marshes of the Scheldt estuary. Arsenic content was determined in soils sampled at 4 sampling depths in 11 marshes, together with other physicochemical characteristics. Subsequently, a greenhouse experiment was set up in which pore water arsenic (As) concentrations were measured 4 times in a 298-day period in 4 marsh soils at different sampling depths (10, 30, 60 and 90 cm) upon adjusting the water table level to 0, 40 and 80 cm below the surface of these soils. The As content in the soil varied significantly with sampling depth and location. Clay and organic matter seem to promote As accumulation in the upper soil layer (0-20 cm below the surface), whereas sulfide precipitation plays a significant role at higher sampling depths (20-100 cm below the surface). The As concentrations in the pore water of the greenhouse experiment often significantly exceeded the Flemish soil sanitation thresholds for groundwater. There were indications that As release is not only affected by the reductive dissolution of Fe/Mn oxides, but also by e.g. a direct reduction of As(V) to As(III). Below the water table, sulfide precipitation seems to lower As mobility when reducing conditions have been sufficiently established. Above the water table, sulfates and bicarbonates induce As release from the solid soil phase to the pore water.

The fate of nitrite and nitrate during anaerobic digestion.

Anaerobic digestion is widely used to produce renewable energy. However, the main drawback is the limited conversion efficiency of organic matter. Applying an advanced oxidation process as a digestate post-treatment is able to increase this conversion efficiency but will also lead to the oxidation of ammonium to nitrite or nitrate. In this lab-scale study, the fate of the latter in the digester was investigated. Nitrite and nitrate were therefore added in concentrations that could arise from rate-limiting ammonium concentrations (1.25-5 g L-1 N). The study clearly demonstrated that nitrite and nitrate were denitrified during the subsequent digestion process resulting in the formation of nitrogen gas. After a concentration-dependent adaptation period, in which some biogas was produced, the added nitrite was denitrified in amounts proportional to the amounts of electron donor present. This denitrification, however, strongly reduces the possibility that Anammox bacteria can develop. Nitrate was also denitrified in amounts proportional to the amounts of electron donor, but biogas production was not completely blocked in this case. Moreover, high concentrations of nitrite and nitrate inhibited their own denitrification. The methane formed was used as electron donor for the further denitrification of nitrate and nitrite when no other readily available electron donor was present. After addition of either nitrite or nitrate and their denitrification, the biogas production did not recover properly.

Production and performance of bio-based mineral fertilizers from agricultural waste using ammonia (stripping-)scrubbing technology.

Development and optimization of nutrient recovery technologies for agricultural waste is on the rise. The full scale adoption of these technologies is however hindered by complex legal aspects that result from lack of science-based knowledge on characterization and fertilizer performance of recovered end-products. Ammonium sulfate (AS) and ammonium nitrate (AN), end-products of (stripping-)scrubbing technology, are currently listed by the European Commission as high priority products with the potential of replacing synthetic N fertilizers. The legal acceptance of AS and AN will be highly dependent on critical mass of scientific evidence. This study describes four different (stripping-)scrubbing pathways to recover ammonia with an aim to (i) assess product characteristics of ammonium nitrate (AN) and ammonium sulfate (AS) produced from different installations, (ii) evaluate fertilizer performance of recovered end-products in greenhouse (Lactuca sativa L.) and full field (Zea mays L.) scale settings and (iii) compare the observed performances with other published studies. Results have indicated that the recovered products might have a different legal status, as either mineral N fertilizer or yet as animal manure, depending on the used (stripping-)scrubbing process pathway. Nevertheless, no significant differences in respect to product characterization and fertilizer performance of AN and AS have been identified in this study as compared to the conventional use of synthetic N fertilizers. This indicates that recovered AS and AN are valuable N sources and therefore might be used as N fertilizers in crop cultivation.

Effect of biodegradable amendments on uranium solubility in contaminated soils.

Chelate-assisted phytoextraction has been proposed as a potential tool for phytoremediation of U contaminated sites. In this context, the effects of five biodegradable amendments on U release in contaminated soils were evaluated. Three soils were involved in this study, one with a relatively high background level of U, and two which were contaminated with U from industrial effluents. Soils were treated with 5 mmol kg(-1) dry weight of either citric acid, NH(4)-citrate/citric acid, oxalic acid, S,S-ethylenediamine disuccinic acid or nitrilotriacetic acid. Soil solution concentration of U was monitored during 2 weeks. All amendments increased U concentration in soil solution, but citric acid and NH(4)-citrate/citric acid mixture were most effective, with up to 479-fold increase. For oxalic acid, S,S-ethylenediamine disuccinic acid and nitrilotriacetic acid, the increase ranged from 10-to 100-fold. The highest concentrations were observed 1 to 7 days after treatment, after which U levels in soil solution gradually decreased. All amendments induced a temporary increase of soil solution pH and TOC that could not be correlated with the release of U in the soil solution. Thermodynamic stability constants (log K) of complexes did not predict the relative efficiency of the selected biodegradable amendments on U release in soil solution. Amendments efficiency was better predicted by the relative affinity of the chelate for Fe compared to U.

Degradability of ethylenediaminedisuccinic acid (EDDS) in metal contaminated soils: implications for its use soil remediation.

Previous research has identified ethylenediaminedisuccinate (EDDS) as a promising biodegradable alternative for persistent compounds such as EDTA for application in soil washing or enhanced phytoextraction of heavy metals. This study examines heavy metal mobilization in three polluted soils varying in soil composition, with specific attention for competitive behaviour for complexation between the various metals and major elements, such as Al, Fe, Mn, Ca and Mg. In addition, amendment biodegradability was compared between the different soil types. The selected soils included a moderately contaminated calcareous clayey soil, a dredged sediment derived surface soil with similar soil characteristics yet more heavily polluted with Cd, Cr and Zn, and a sandy soil moderately contaminated by historical smelter activity (atmospheric deposition). Biodegradability of EDDS in the three soils varied distinctly. This was mainly expressed in the duration of the lag phase prior to metal complex degradation, and not so much in the half life when degradation effectively did set in. Differences in the lag phase were attributed to differences in soil pollution. However, EDDS was fully degraded within a period of 54 d in all soils regardless of initial delay. Assessment of the cation mobilisation patterns in the three soils under study revealed that mainly Ca, Fe and Al can reduce effectiveness of heavy metal mobilisation by competition for complexation.

Impact of organic amendments (biochar, compost and peat) on Cd and Zn mobility and solubility in contaminated soil of the Campine region after three years.

To determine the long-term impact of organic amendments on metal (Cd and Zn) immobilization, soil from the Campine region was amended with holm oak-derived biochar, compost, and peat, and monitored over a 3-year period. Pot experiments were conducted by mixing the amendments independently at 2% and 4% (g/g) with the soil. The mobility and solubility of metals in the treatments were assessed by means of rhizon soil moisture samplers, sequential BCR extractions, and diffusive gradient in thin films (DGT). Over the three-year period, the 2% biochar addition resulted in an average decrease in pore water concentration of 40% for Cd and 48% for Zn whereas the 4% addition led to an average decrease of 66% for Cd and 77% for Zn. The immobilization effect in the biochar treatments was attributed to the consistently higher pH and lower concentrations of dissolved organic carbon (DOC) in the soil. The latter may have been caused by sorption of DOC onto the surface of biochar thereby increasing its negatively charged functional groups that are able to sorb cations. On the other hand, compost and peat had the unwanted effect of significantly increasing the concentrations of Cd and Zn in the soil pore water. This was partly due to the formation of soluble organo-metallic complexes as significantly higher DOC concentrations were found in the compost and peat treatments. Results from the DGT measurements, after a 24 h deployment time, revealed a low resupply (R ≤ 0.4) of Cd and Zn from the solid phase to the soil solution in both amended and unamended soil. This suggests a case of slow metal desorption kinetics in the soil that was relatively unchanged by the presence of organic amendments.

Accumulation of metals in a horizontal subsurface flow constructed wetland treating domestic wastewater in Flanders, Belgium.

This study assessed the accumulation of metals in a horizontal subsurface flow constructed wetland treating domestic wastewater of 350 PE after three years of operation. Metal concentrations in the influent wastewater, effluent, sediment, leaves, stems, and belowground biomass of Phragmites australis were analysed. Spatial variations were assessed by sampling at increasing distance from the inlet and at different positions across the width of the reed bed. All metals except Fe and Mn were efficiently removed in the CW, total metal concentrations in the effluent complied with basic environmental quality standards for surface water, and dissolved metal concentrations were often lower than analytical detection limits. Removal efficiencies varied between 49% for Ni and 93% for Al. Export of dissolved Mn and particulate Fe occurred, probably related to redox conditions in the sediment. After 3 years of operation, the sediment in the inlet area was significantly contaminated with Zn, Cu, and Cd, whereas Pb could form a contamination problem within the near future. The Cr and Ni levels in the sediment were low throughout the entire reed bed. At this stage of operation, the contamination problem was still situated within the inlet area and metal concentrations in the sediment decreased towards background values further along the treatment path. An exponential decrease of the metal mass in the sediment and belowground biomass was seen for all metals except Mn. Contrary to the other metals, Mn concentrations in the sediment increased with distance. For all metals, less than 2% of the mass removed from the wastewater after passage through the reed bed is accumulated in the aboveground reed biomass. The sediment acts as the primary sink for metals.

Cu sorption on Phragmites australis leaf and stem litter: a kinetic study.

Decaying organic matter plays an important role in the cycling of metals in wetland ecosystems. Sorption kinetics of Cu(II) on Phragmites australis leaf and stem litter were studied. Fresh leaf and stem litter was sampled from a surface flow wetland at the end of the growing season. The effect of decomposition stage was studied with litter that had been decomposing for a period of 5 months. The Lagergren pseudo-first-order model, the pseudo-second-order model, the Elovich equation and two diffusion models based on spherical intra-particle diffusion were fitted to the experimental data. The sorption capacity was significantly affected by the decomposition of the litter. The sorption process was best described by the pseudo-second-order kinetics (R(2) approximately 0.99) but the rate constant was strongly dependent on the initial Cu concentration. The intra-particle diffusion model fitted the data only slightly less (R(2)>0.95) than the pseudo-second-order model. A theoretical comparison revealed that the good fit with the pseudo-second-order kinetics could be indicative of intra-particle diffusion. Sorption kinetics observed for the leaf and stem litter at different metal concentrations showed a fast initial sorption followed by a slow sorption phase.

Fertilizer performance of liquid fraction of digestate as synthetic nitrogen substitute in silage maize cultivation for three consecutive years.

Following changes over recent years in fertilizer legislative framework throughout Europe, phosphorus (P) is taking over the role of being the limiting factor in fertilizer application rate of animal manure. This results in less placement area for spreading animal manure. As a consequence, more expensive and energy demanding synthetic fertilizers are required to meet crop nutrient requirements despite existing manure surpluses. Anaerobic digestion followed by mechanical separation of raw digestate, results in liquid fraction (LF) of digestate, a product poor in P but rich in nitrogen (N) and potassium (K). A 3-year field experiment was conducted to evaluate the impact of using the LF of digestate as a (partial) substitute for synthetic N fertilizer. Two different fertilization strategies, the LF of digestate in combination with respectively animal manure and digestate, were compared to the conventional fertilization regime of raw animal manure with synthetic fertilizers. Results from the 3-year trial indicate that the LF of digestate may substitute synthetic N fertilizers without crop yield losses. Through fertilizer use efficiency assessment it was observed that under-fertilization of soils with a high P status could reduce P availability and consequently the potential for P leaching. Under conditions of lower K application, more sodium was taken up by the crop. In arid regions, this effect might reduce the potential risk of salt accumulation that is associated with organic fertilizer application. Finally, economic and ecological benefits were found to be higher when LF of digestate was used as a synthetic N substitute. Future perspectives indicate that nutrient variability in bio-based fertilizers will be one of the greatest challenges to address in the future utilization of these products.

Mild hydrothermal conditioning prior to torrefaction and slow pyrolysis of low-value biomass.

The aim of this research was to establish whether hydrothermal conditioning and subsequent thermochemical processing via batch torrefaction or slow pyrolysis may improve the fuel quality of grass residues. A comparison in terms of fuel quality was made of the direct thermochemical processing of the feedstock versus hydrothermal conditioning as a pretreatment prior to thermochemical processing. Hydrothermal conditioning reduced ash content, and particularly nitrogen, potassium and chlorine contents in the biomass. The removal of volatile organic matter associated with thermochemical processes can increase the HHV to levels of volatile bituminous coal. However, slow pyrolysis only increased the HHV of biomass provided a low ash content (<6%) feedstock was used. In conclusion, hydrothermal conditioning can have a highly positive influence on the efficiency of thermochemical processes for upgrading low-value (high-ash) biomass to a higher quality fuel.

Availability of heavy metals for uptake by Salix viminalis on a moderately contaminated dredged sediment disposal site.

Extractability of Cd, Cr, Cu, Ni, Pb, and Zn in a dredged sediment disposal site was assessed using single extraction procedures (H2O; 0.01 M CaCl2; 1 M NH4OAc; NH4OAc-EDTA; CaCl2-TEA-DTPA). Only Cd and Zn were found to exceed statutory threshold values for total content. The field was planted with Salix viminalis "Orm" and accumulation of heavy metals in bark, leaves, roots, and wood was evaluated at seven sampling locations along an observed gradient in texture and pollution. Biomass production was high, ranging from 13.2 to 17.8 t ha(-1) y(-1) dry weight. Metal accumulation in aboveground plant parts was low, amounting to the following annually extracted mass of metals per ha: 5034 g Zn, 83 g Cd, 145 g Cu, 83 g Pb, 12 g Ni and 6 g Cr. The use of accumulating clones and the use of soil amendments might enhance extraction efficiency in future research.

Potential of Brassic rapa, Cannabis sativa, Helianthus annuus and Zea mays for phytoextraction of heavy metals from calcareous dredged sediment derived soils.

Remediation of soil pollution is one of the many current environmental challenges. Anthropogenic activity has resulted in the contamination of extended areas of land, the remediation of which is both invasive and expensive by conventional means. Phytoextraction of heavy metals from contaminated soils has the prospect of being a more economic in situ alternative. In addition, phytoextraction targets ecotoxicologically the most relevant soil fraction of these metals, i.e. the bioavailable fraction. Greenhouse experiments were carried out to evaluate the potential of four high biomass crop species in their potential for phytoextraction of heavy metals, with or without with the use of soil amendments (EDTA or EDDS). A calcareous dredged sediment derived surface soil, with high organic matter and clay content and moderate levels of heavy metal pollution, was used in the experiments. No growth depression was observed in EDTA or EDDS treated pots in comparison to untreated controls. Metal accumulation was considered to be low for phytoextraction purposes, despite the use of chelating agents. The low observed shoot concentrations of heavy metals were attributed to the low phytoavailability of heavy metals in this particular soil substrate. The mobilising effects induced by EDTA in the soil were found to be too long-lived for application as a soil amendment in phytoextraction. Although EDDS was found to be more biodegradable, higher effect half lives were observed than reported in literature or observed in previous experiments. These findings caution against the use of any amendment, biodegradable or otherwise, without proper investigation of its effects and the longevity thereof.