Gijs Du Laing

Floc-based sequential partial nitritation and anammox at full scale with contrasting N2O emissions

New Activated Sludge (NAS(®)) is a hybrid, floc-based nitrogen removal process without carbon addition, based on the control of sludge retention times (SRT) and dissolved oxygen (DO) levels. The aim of this study was to examine the performance of a retrofitted four-stage NAS(®) plant, including on-line measurements of greenhouse gas emissions (N(2)O and CH(4)). The plant treated anaerobically digested industrial wastewater, containing 264 mg N L(-1), 1154 mg chemical oxygen demand (COD) L(-1) and an inorganic carbon alkalinity of 34 meq L(-1). The batch-fed partial nitritation step received an overall nitrogen loading rate of 0.18-0.22 kg N m(-3) d(-1), thereby oxidized nitrogen to nitrite (45-47%) and some nitrate (13-15%), but also to N(2)O (5.1-6.6%). This was achieved at a SRT of 1.7 d and DO around 1.0 mg O(2) L(-1). Subsequently, anammox, denitrification and nitrification compartments were followed by a final settler, at an overall SRT of 46 d. None of the latter three reactors emitted N(2)O. In the anammox step, 0.26 kg N m(-3) d(-1) was removed, with an estimated contribution of 71% by the genus Kuenenia, which constituted 3.1% of the biomass. Overall, a nitrogen removal efficiency of 95% was obtained, yielding a dischargeable effluent. Retrofitting floc-based nitrification/denitrification with carbon addition to NAS(®) allowed to save 40% of the operational wastewater treatment costs. Yet, a decrease of the N(2)O emissions by about 50% is necessary in order to obtain a CO(2) neutral footprint. The impact of emitted CH(4) was 20 times lower.

Arsenic metabolism by human gut microbiota upon in vitro digestion of contaminated soils.

Background Speciation analysis is essential when evaluating risks from arsenic (As) exposure. In an oral exposure scenario, the importance of presystemic metabolism by gut microorganisms has been evidenced with in vivo animal models and in vitro experiments with animal microbiota. However, it is unclear whether human microbiota display similar As metabolism, especially when present in a contaminated matrix. Objectives We evaluated the metabolic potency of in vitro cultured human colon microbiota toward inorganic As (iAs) and As-contaminated soils. Methods A colon microbial community was cultured in a dynamic model of the human gut. These colon microbiota were incubated with iAs and with As-contaminated urban soils. We determined As speciation analysis using high-performance liquid chromatography coupled with inductively coupled plasma mass spectrometry. Results We found a high degree of methylation for colon digests both of iAs (10 μg methylarsenical/g biomass/hr) and of As-contaminated soils (up to 28 μg/g biomass/hr). Besides the formation of monomethylarsonic acid (MMAV), we detected the highly toxic monomethylarsonous acid (MMAIII). Moreover, this is the first description of microbial thiolation leading to monomethylmonothioarsonic acid (MMMTAV). MMMTAV, the toxicokinetic properties of which are not well known, was in many cases a major metabolite. Conclusions Presystemic As metabolism is a significant process in the human body. Toxicokinetic studies aiming to completely elucidate the As metabolic pathway would therefore benefit from incorporating the metabolic potency of human gut microbiota. This will result in more accurate risk characterization associated with As exposures.

Arsenic in cooked rice: Effect of chemical, enzymatic and microbial processes on bioaccessibility and speciation in the human gastrointestinal tract

Rice, used as staple food for half of the world population, can easily accumulate arsenic (As) into its grain, which often leads to As contamination. The health risk induced by presence of As in food depends on its release from the food matrix, i.e., its bioaccessibility. Using an in vitro gastrointestinal simulator, we incubated two types of cooked rice (total As: 0.389 and 0.314 mg/kg). Arsenic bioaccessibility and speciation changes were determined upon gastrointestinal digestion. Washing with deionized water and cooking did not result in changes of As speciation in the rice although the arsenic content dropped by 7.1-20.6%. Arsenic bioaccessibility of the cooked rice in the small intestine ranged between 38 and 57%. Bioaccessibility slightly increased during digestion in the simulated small intestine and decreased with time in the simulated colon. Significant speciation changes were noted in the simulated colon, with trivalent monomethylarsonate (MMA(III)) becoming an important species.

Heavy metal contents (Cd, Cu, Zn) in spiders (Pirata piraticus) living in intertidal sediments of the river Scheldt estuary (Belgium) as affected by substrate characteristics

Metals are transferred into the food web by ground-dwelling organisms, among others. This study aimed to identify the most important factors that determine the bioavailability of heavy metals to the spider Pirata piraticus living in the intertidal sediments of the Scheldt estuary (Flanders, Belgium). At five locations, which represent a varying degree of metal contamination and salinity, the superficial layer of sediments was characterised for physico-chemical properties and heavy metal (Cd, Cu, Zn) content and extractability. Spiders were sampled at the same locations and analysed for Cd, Cu and Zn. Higher Cd, Cu and Zn contents were found in spiders on sites with lower total metal contents in the sediment. These sites were closest to the river mouth and were characterised by a higher salinity. Significant, positive correlations were found between the chloride content of the sediments and the Cd, Cu and Zn content of P. piraticus. Similarly, a strong relationship was observed between the ratio of exchangeable Cd and Zn to the total cation exchange capacity and the contents of these elements in P. piraticus. These field data indicated that salinity, cation exchange capacity and exchangeable metal contents were of most importance in determining bioavailability of heavy metals in these intertidal sediments.

Factors affecting metal concentrations in the upper sediment layer of intertidal reedbeds along the river Scheldt

Factors that play a role in determining metal accumulation in sediments of 26 intertidal marshes which are mainly vegetated by reed plants (Phragmites australis) were assessed along the Scheldt estuary (Belgium and The Netherlands). In the upper 20 cm sediment layer, several physico-chemical properties (clay, silt and sand content, organic matter, carbonate and chloride content, pH and conductivity) and aqua regia extractable metals (Cd, Cr, Cu, Ni, Pb, Zn) were determined. The sediments were significantly contaminated with trace metals. The Cd concentrations often exceeded the Flemish soil remediation thresholds for nature areas, whereas Cr, Cu and Zn levels indicated moderate contamination. Pb concentrations occasionally were high, whereas Ni concentrations leaned towards background values. Organic matter was the single most important predictor variable for total metal contents in regression models, except for Cr. Additional significant predictor variables were clay or chloride content, depending on the metal. Observed metal concentrations at sites within a range of a few km from specific point-sources of metals (e.g. shipyards, industrial areas with metallurgic activities, affluents, major motorways) were somewhat higher than predicted by the models, whereas they were lower than predicted at sites which are regularly subjected to flooding by water of high salinity. The ratio between observed and predicted concentrations seems to be a valuable tool for the identification of areas which are specifically impacted by point sources.

Accumulation and fractionation of trace metals in a Tunisian calcareous soil amended with farmyard manure and municipal solid waste compost

A field plots experiment was carried out to assess the effects of repeated application of municipal solid waste compost in comparison to farmyard manure on the accumulation and distribution of trace metals, as well as organic carbon and nitrogen in Tunisian calcareous soil. Compared with untreated soil, the application of the two organic amendments significantly increased the organic carbon and nitrogen contents of the soil. Particle-size fractionations showed that carbon and nitrogen were mainly found to occur in the macro-organic matter fraction (80%). The two organic amendments significantly increased organic carbon in the macro-organic and mineral >150 microm fraction and the 150-50 microm fraction, as well as the organic nitrogen in 150-50 microm and macro-organic fraction. Compared with farmyard manure, municipal solid waste compost significantly increased total Cd, Cu, Pb and Zn contents in the topsoil. These trace metals were mainly present in the macro-organic matter fraction. Significant increases of Cu, Zn and Pb were detected in the 150-50 microm, <50 microm and macro-organic fractions after application of municipal solid waste compost. A significant increase of Cd content was only observed in the 150-50 microm fraction. The trace metals also showed different fractionation patterns when the BCR sequential extraction scheme was applied on untreated and compost-treated soil. The residual fraction was found to be the major fraction, especially for Cu, Cr, Ni and Zn. In contrast, Cd was mainly present in the acid-extractable and reducible fraction, whereas Pb was mainly associated with the reducible fraction.

Dynamics of mercury fluxes and their controlling factors in large Hg-polluted floodplain areas.

Environmental pollution by mercury (Hg) is a considerable environmental problem world-wide. Due to the occurrence of Hg volatilization from their soils, floodplains can function as an important source of volatile Hg. Soil temperature and soil water content related to flood dynamics are considered as important factors affecting seasonal dynamics of total gaseous mercury (TGM) fluxes. We quantified seasonal variations of TGM fluxes and conducted a laboratory microcosm experiment to assess the effect of temperature and moisture on TGM fluxes in heavily polluted floodplain soils. Observed TGM emissions ranged from 10 to 850 ng m(-2) h(-1) and extremely exceeded the emissions of non-polluted sites. TGM emissions increased exponentially with raised air and soil temperatures in both field (R(2): 0.49-0.70) and laboratory (R(2): 0.99) experiments. Wet soil material showed higher TGM fluxes, whereas the role of soil water content was affected by sampling time during the microcosm experiments.

Heavy metal mobility in intertidal sediments of the Scheldt estuary : Field monitoring

The current paper aims to check whether the factors affecting metal mobility in intertidal sediments and floodplain soils of the river Scheldt, as identified under controlled greenhouse conditions in previous studies, also play a similar role under variable field conditions. Moreover, we aimed to assess the importance of these factors as a function of sampling time and depth, with respect to the natural variations in water table levels. This field monitoring revealed that the mobility of metals in intertidal sediments of the Scheldt estuary indeed are affected by factors which were identified to affect the metal fate in the upper sediment layer in previous greenhouse experiments. However, the effects were often less pronounced under field conditions. This can be attributed to the lower sampling resolution, the occurrence of interactions between factors, the disturbance of microbial communities during setup of greenhouse experiments and the more moderate environmental conditions in the field, affecting microbial and enzymatic activities. At most of the sampled wetlands, the level of the water table fluctuated only slightly during fall, winter and spring, whereas it decreased substantially during summer, especially at the sites with more sandy sediments. The highest sulphide concentrations were found at the sites where the water table level never decreased considerably. These sulphides primarily suppress the availability of Cd, Cu, Ni and Zn. Organic complexation resulted in the mobilisation of Cu, Ni and Cr. The concentrations of Cd, Ni and Zn in the pore water were affected by Fe/Mn oxide reduction, whereas Cd and Zn concentrations appeared to be also affected by the salinity.

Soil‐solution speciation of CD as affected by soil characteristics in unpolluted and polluted soils

Total metal content by itself is insufficient as a measure to indicate actual environmental risk. Understanding the mobility of heavy metals in the soil and their speciation in the soil solution is of great importance for accurately assessing environmental risks posed by these metals. In a first explorative study, the effects of general soil characteristics on Cd mobility were evaluated and expressed in the form of empirical formulations. The most important factors influencing mobility of Cd proved to be pH and total soil content. This may indicate that current legislation expressing the requirement for soil sanitation in Flanders (Belgium) as a function of total soil content, organic matter, and clay does not successfully reflect actual risks. Current legal frameworks focusing on total content, therefore, should be amended with criteria that are indicative of metal mobility and availability and are based on physicochemical soil properties. In addition, soil-solution speciation was performed using two independent software packages (Visual Minteq 2.23 and Windermere Humic Aqueous model VI [WHAM VI]). Both programs largely were in agreement in concern to Cd speciation in all 29 soils under study. Depending on soil type, free ion and the organically complexed forms were the most abundant species. Additional inorganic soluble species were sulfates and chlorides. Minor species in solution were in the form of nitrates, hydroxides, and carbonates, the relative importance of which was deemed insignificant in comparison to the four major species.

Metal Accumulation in Intertidal Marshes: Role of Sulphide Precipitation

We assessed short-term temporal and spatial variation of metal contents in the upper 100 cm sediment profile of intertidal marshes vegetated by common reed (Phragmites australis) along the Scheldt estuary in Belgium. The upper 0–100 cm sediment profile was sampled in three reedbeds at 56, 94, and 131 km from the river mouth. Sampling was repeated five times, at approximately two month intervals. Sediment properties such as texture and chloride, carbonate and organic matter content differed among locations. Metal accumulation, which is primarily due to association of metals with organic matter and clay in the surface sediment layer, seemed to be supplemented by an accumulation of sulphide precipitates deeper in the sediments. The depth at which sulphide precipitation significantly contributed to metal accumulation depended on the sampling location, and varied from less than 5 cm in clayey, organic sediments to more than 1 m in sandy sediments. Temporal variation of Cu, Cd, Pb, and Zn concentrations could only be linked to newly formed sulphides or sulphide oxidation at the sites with the lowest sulphide content. At sampling sites containing high sulphide amounts, variations should be primarily attributed to metal exchange and the presence of mobile metal complexes. Litter decomposition at the end of the growing season could hereby play a significant role.