A quantum cascade laser infrared spectrometer for CO2 stable isotope analysis: Field implementation at a hydrocarbon contaminated site under bio-remediation

Real-time methods to monitor stable isotope ratios of CO_2 are needed to identify biogeochemical origins of CO_2 emissions from the soil–air interface. An isotope ratio infra-red spectrometer(IRIS) has been developed to measure CO_2 mixing ratio with δ~13C isotopic signature, in addition to mixing ratios of other greenhouse gases(CH_4, N2_O). The original aspects of the instrument as well as its precision and accuracy for the determination of the isotopic signature δ~13C of CO_2 are discussed. A first application to biodegradation of hydrocarbons is presented, tested on a hydrocarbon contaminated site under aerobic bio-treatment. CO_2 flux measurements using closed chamber method is combined with the determination of the isotopic signature δ~13C of the CO_2 emission to propose a non-intrusive method to monitor in situ biodegradation of hydrocarbons. In the contaminated area, high CO_2 emissions have been measured with an isotopic signature δ~13C suggesting that CO_2 comes from petroleum hydrocarbon biodegradation.This first field implementation shows that rapid and accurate measurement of isotopic signature of CO_2 emissions is particularly useful in assessing the contribution of contaminant degradation to the measured CO_2 efflux and is promising as a monitoring tool for aerobic bio-treatment.     

Predictive statistical modelling of cadmium content in durum wheat grain based on soil parameters

Regulatory limits on cadmium (Cd) content in food products are tending to become stricter, especially in cereals, which are a major contributor to dietary intake of Cd by humans. This is of particular importance for durum wheat, which accumulates more Cd than bread wheat. The contamination of durum wheat grain by Cd depends not only on the genotype but also to a large extent on soil Cd availability. Assessing the phytoavailability of Cd for durum wheat is thus crucial, and appropriate methods are required. For this purpose, we propose a statistical model to predict Cd accumulation in durum wheat grain based on soil geochemical properties related to Cd availability in French agricultural soils with low Cd contents and neutral to alkaline pH (soils commonly used to grow durum wheat). The best model is based on the concentration of total Cd in the soil solution, the pH of a soil CaCl₂ extract, the cation exchange capacity (CEC), and the content of manganese oxides (Tamm’s extraction) in the soil. The model variables suggest a major influence of cadmium buffering power of the soil and of Cd speciation in solution. The model successfully explains 88% of Cd variability in grains with, generally, below 0.02 mg Cd kg^?1 prediction error in wheat grain. Monte Carlo cross-validation indicated that model accuracy will suffice for the European Community project to reduce the regulatory limit from 0.2 to 0.15 mg Cd kg^?1 grain, but not for the intermediate step at 0.175 mg Cd kg^?1. The model will help farmers assess the risk that the Cd content of their durum wheat grain will exceed regulatory limits, and help food safety authorities test different regulatory thresholds to find a trade-off between food safety and the negative impact a too strict regulation could have on farmers.

     

The relation between the estimated dietary intake of PCDD/Fs and levels in blood in a Flemish population (50-65 years)

Dioxin-like activity was measured in the serum of 1425 Flemish men and women via the CALUX assay. The adults, aged between 50 and 65 years, participated in a large biomonitoring program, executed by the Flemish Center of Expertise for Environment and Health between 2002 and 2006. Within the context of this biomonitoring program also dietary intake of dioxin-like contaminants was assessed through a food frequency questionnaire. The relation between the estimated dietary intake and the dioxin-like activity in serum was evaluated using multivariate analyses: a logistic model was performed on the total population, while a linear regression analysis was done on the subsample with quantifiable dioxin activity levels in serum. Region, gender, age, BMI, smoking status, as well as dietary habits were entered in the model, with dioxin level as an outcome estimate. Both the logistic and linear model confirmed the contribution of dietary intake to the dioxin activity measured in serum. Also BMI and region were found to be associated with dioxin activity levels.     

Delimiting synchronous populations from monitoring data

We propose to investigate spatial synchrony in population dynamics from monitoring data. We develop a statistical procedure to delineate populations of sites with synchronous dynamics from short time series. The procedure relies on a new norm, the synchronous total variation norm, which promotes synchrony in the estimation of the sites dynamics. The method is tested on some synthetic data sets and is applied on data from the French breeding bird monitoring program.     

Linking intra-seasonal variations in climate and tree-ring δC: A functional modelling approach

Stable carbon isotopic composition (δ¹³C) in tree rings is a widely recognized tool for climate reconstruction, and several works suggest that seasonal information can be extracted from intra-ring δ¹³C variations. In this study, we explored the link between climate and intra-seasonal oak ring δ¹³C using a process-based modelling approach. The ISOCASTANEA model was developed to compute the seasonal dynamics of tree-ring δ¹³C for deciduous species from half-hourly climatic data by accounting for photosynthetic discrimination and carbon translocation and allocation at the tree scale and in tree rings.The model was applied from March 2005 to December 2007 in a 150-year-old deciduous oak forest. Canopy photosynthesis and stomatal conductance were calibrated using H₂O and CO₂ fluxes measured by the eddy flux technique, and simulated δ¹³C values were compared to seasonal patterns of total organic matter δ¹³C measured in tree rings for 2006 and 2007 at the same site. With the inclusion of carbon translocation and with regard to ¹³C enrichment of starch compared to soluble sugars, the model can reasonably simulate the intra-seasonal and inter-annual variability of tree-ring δ¹³C using the same parameter values for 2006 and 2007. The amplitude of the seasonal carbon isotope pattern in tree rings was influenced by both photosynthetic and post-photosynthetic processes (starch enrichment and reserve use). The δ¹³C variations in the early part of the ring, i.e., mainly in the earlywood, were related mostly to carbohydrate metabolism, although diluted information about environmental conditions during the previous year could also be found. The last part of the ring, consisting mainly of latewood, was found to be a good recorder of current-year environmental conditions, in particular relative humidity, at a fine temporal resolution when the growth rate was high. The sensitivity of the δ¹³C in the early part of the ring to carbohydrate metabolism suggests that intra-ring δ¹³C could be used to explore the relationship between tree decline or mortality and carbohydrate deficiency.     

Effects of increasing temperatures on biomarker responses and accumulation of hazardous substances in rope mussels (Mytilus galloprovincialis) from Bizerte lagoon

This study examined the influence of increasing temperatures in spring and summer on biochemical biomarkers in Mytilus galloprovincialis mussels sampled from Bizerte lagoon (northern Tunisia). Spatial and seasonal variations in a battery of seven biomarkers were analyzed in relation to environmental parameters (temperature, salinity, and pH), physiological status (condition and gonad indexes), stress on stress (SoS), and chemical contaminant levels (heavy metals, polycyclic aromatic hydrocarbons (PAHs), and PCBs) in digestive glands. Integrated biological response (IBR) was calculated using seven biomarkers (acetylcholinesterase (AChE), benzo[a]pyrene hydroxylase (BPH), multixenobiotic resistance (MXR), glutathione S-transferase (GST), catalase (CAT), malondialdehyde (MDA), and metallothioneins (MT). Seasonal variations in biological response were determined during a critical period between spring and summer at two sites, where chemical contamination varies by a factor of 2 for heavy metals and a factor 2.5 for PAHs. The analysis of a battery of biomarkers was combined with the measurement of physiological parameters at both sites, in order to quantify a maximum range of metabolic regulation with a temperature increase of 11 °C between May and August. According to our results, the MT, MDA, CAT, and AChE biomarkers showed the highest amplitude during the 11 °C rise, while the BPH, GST, and MXR biomarkers showed the lowest amplitude. Metabolic amplitude measured with the IBR at Menzel Abdelrahmen—the most severely contaminated station—revealed the highest metabolic stress in Bizerte lagoon in August, when temperatures were highest 29.1 °C. This high metabolic rate was quantified for each biomarker in the North African lagoon area and confirmed in August, when the highest IBR index values were obtained at the least contaminated site 2 (IBR = 9.6) and the most contaminated site 1 (IBR = 19.6). The combined effects of chemical contamination and increased salinity and temperatures in summer appear to induce a highest metabolic adaptation response and can therefore be used to determine thresholds of effectiveness and facilitate the interpretation of monitoring biomarkers. This approach, applied during substantial temperature increases at two sites with differing chemical contamination, is a first step toward determining an environmental assessment criteria (EAC) threshold in a North African lagoon.     

Identification of 1-methyloctyl butanoate as the major sex pheromone component from females of the saddle gall midge,Haplodiplosis marginata (Diptera: Cecidomyiidae)

The saddle gall midge, Haplodiplosis marginata (von Roser) (Diptera: Cecidomyiidae), has undergone a resurgence recently as a pest of cereals in Belgium and other European countries. An effective monitoring tool of saddle gall midge flights is needed to understand the enigmatic population dynamics of this pest, and to design an integrated management strategy. Therefore, volatile compounds emitted by females (alkan-2-ols and alk-2-yl butanoates) were identified, and the chirality of the emitted esters was determined to be the R absolute configuration. In field-trapping experiments, racemic non-2-yl butanoate attracted substantial numbers of H. marginata males. Thus, this compound will be useful in baited traps for monitoring seasonal flight patterns, and improving integrated management of the saddle gall midge in agricultural systems.