Chelate assisted phytoextraction of heavy metals from soil. Effect, mechanism, toxicity, and fate of chelating agents

The low-cost, plant-based phytoextraction technique has often been described as a promising technique to remediate heavy metal contaminated agricultural land. The application of chelating agents has shown positive effects in increasing the solubility of heavy metals in soil and therefore in enhancing phytoextraction. This paper gives an overview of the chelating agents applied in recent studies. Various synthetic aminopolycarboxylic acids, such as ethylene diamine tetraacetic acid, and natural ones such as, ethylene diamine disuccinate and nitrilotriacetic acid, are described. Additionally, results of the application of natural low molecular weight organic acids, such as citric and tartaric acid are given. The effectiveness of these different chelating agents varies according to the plant and the heavy metals used. Furthermore, a focus is laid on the chelating agents fate after application and on its toxicity to plants and soil microorganisms, as well as it degradation. The rate of degradation is of great importance for the future of chelate assisted phytoextraction as it has a direct impact on the leaching probability. An effective prevention of leaching will be crucial for the acceptance and the economic breakthrough of enhanced phytoextraction, but a satisfactory solution to this key issue has so far not been found. Possibly further experiments in the field of enhanced phytoextraction will be able to solve this major problem, but over decades various greenhouse experiments and recently field experiments have resulted in different observations. Therefore, it is questionable if further research in this direction will lead to a promising solution. Phytoextraction has possibly reached a turning point in which it should distance itself from chelate assisted phytoextraction and focus on alternative options.     

Aerobic biodegradation of organotin compounds in activated sludge batch reactors

The biodegradation behavior of four organotin (OT) compounds, namely tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT) and triphenyltin (TPhT), was studied in lab-scale activated sludge batch reactors. The activated sludge was spiked with the OT compounds at a level of 100 microg l(-1) as Sn. Determination of the OT compounds by GC-FPD after ethylation in the dissolved and particulate phase revealed that 24 h after the start of the experiments, almost the total of OT compounds has been removed from the dissolved phase and is associated with the suspended solids. Calculation of mass balance in batch reactors showed that OT compounds biodegradation was performed via a sequential dealkylation process. Removals due to biodegradation were differentiated according to the parent compound. In experiments with non-acclimatized biomass, a percentage of 27.1, 8.3, 73.8 and 51.3 was still present as TBT, DBT, MBT and TPhT, respectively, at the end of the experiment (18th day). Half-lives (t1/2) of 10.2 and 5.1 days were calculated for TBT and DBT, respectively, whereas apparent t1/2 values could not be determined for MBT and TPhT (t1/2>18 days). The capacity of activated sludge to biodegrade OT compounds in the absence of supplemental substrate indicated that these compounds can be metabolized as single sources of carbon and energy in activated sludge systems. Excluding TBT, the presence of low concentrations of supplemental substrate did not affect the biodegradation potential of activated sludge. The acclimatization of biomass on OT compounds enhanced significantly biodegradation, resulting in significant decreases of half-lives of OT compounds. As a result in the presence of acclimatized biomass, half-lives of 1.4, 3.6, 9.8 and 5.0 days were calculated for TBT, DBT, MBT and TPhT, respectively.     

Distribution and incorporation mode of the herbicide MCPA in soil derived organo-clay complexes

The incorporation of xenobiotics into soil, especially via covalent bonds or sequestration has a major influence on the environmental behavior including toxicity, mobility, and bioavailability. The incorporation mode of 4-chloro-2-methylphenoxyacetic acid (MCPA) into organo-clay complexes has been investigated under a low (8.5 mg MCPA/kg soil) and high (1000 mg MCPA/kg soil) applied concentration, during an incubation period of up to 120 days. Emphasis was laid on the elucidation of distinct covalent linkages between non-extractable MCPA residues and humic sub-fractions (humic acids, fulvic acids, and humin). The cleavage of compounds by a sequential chemical degradation procedure (OH^?, BBr₃, RuO₄, TMAH thermochemolysis) revealed for both concentration levels ester/amide bonds as the predominate incorporation modes followed by ether linkages. A possible influence of the soil microbial activity on the mode of incorporation could be observed in case of the high level samples. Structure elucidation identified MCPA as the only nonextractable substance, whereas the metabolite 4-chloro-2-methylphenol was additionally found as bioavailable and bioaccessible compound.     

Speciated mercury in size-fractionated particles in Shanghai ambient air

Size-fractionated particles were collected at two sites from July 2004 to April 2006 in Shanghai. The mercury in particles was extracted and divided operationally into four species: exchangeable particulate mercury (EXPM), HCl-soluble particulate mercury (HPM), elemental particulate mercury (EPM) and residual particulate mercury. The total particulate Hg concentration during the study period ranged from 0.07 ng m^?3 to 1.45 ng m^?3 with the average 0.56 ± 0.22 ng m^?3 at site 1, while 0.20 ng m^?3–0.47 ng m^?3 with the average 0.33 ± 0.09 ng m^?3 at site 2, which is far higher than some foreign cities and comparable to some cities with heavy air pollution in China. The Hg mass content also displayed evident size distribution, with higher value in PM_1.6–3.7, somewhat higher or lower than the source profile. EXAM was only found in the summer, HPM have higher percentage in summer and fall rather than in winter and spring. The different mercury species showed different correlation to temperature, relative humidity, wind speed. HPM positively depends on temperature at both sites which implies the importance of mercury transformation on particles. In foggy days TPM increased greatly, but HPM didn't vary greatly as anticipated. Instead, RPM gained a distinguished increase. It demonstrated that aqueous reaction and complex heterogenic reactions in droplet might happen in acidic environment. The correlation of mercury with other pollutants including SO₂, NO₂, CO and PM₁₀ varies with the different mercury forms. Hybrid single-particle lagrangian integrated trajectories (HYSPLIT) model was used to back trace air mass at different representative days and results indicated that transportation from Huabei Plain will increase mercury concentration in winter and fall to some extent. The possible existing compounds and their atmospheric behavior of HPM, EPM and RPM were calculated and the compared to analyze its implication on atmospheric mercury cycle.     

Factors influencing PM10 emissions from road pavement wear

Accelerated pavement wear is one of the major environmental disadvantages of studded tyres in northern regions and results in increased levels of PM₁₀. Measurements of PM₁₀ in a road simulator hall have been used to study the influence of pavement properties, tyre type and vehicle speed on pavement wear. The test set-up included three different pavements (one granite and two quartzite with different aggregate sizes), three different tyre types (studded, non-studded, and summer tyres) and different speeds (30–70 km h^?1). The results show that the granite pavement was more prone to PM₁₀ production compared to the quartzite pavements. Studded winter tyres yield tens of times higher PM₁₀ concentrations compared to non-studded winter tyres. Wear from summer tyres was negligible in comparison. It was also shown that wear is strongly dependent on speed; every 10 km h^?1 increase yielded an increase of the PM₁₀ concentration of 680 μg m^?3 in one of the simulator experiments.     

Persistence of C-labeled atrazine and its residues in a field lysimeter soil after 22 years

Twenty-two years after the last application of ring-¹⁴C-labeled atrazine at customary rate (1.7 kg ha⁻¹) on an agriculturally used outdoor lysimeter, atrazine is still detectable by means of accelerated solvent extraction and LC-MS/MS analysis. Extractions of the 0-10 cm soil layer yielded 60% of the residual ¹⁴C-activity. The extracts contained atrazine (1.0 μg kg⁻¹) and 2-hydroxy-atrazine (42.5 μg kg⁻¹). Extractions of the material of the lowest layer 55-60 cm consisting of fine gravel yielded 93% of residual ¹⁴C-activity, of which 3.4 μg kg⁻¹ was detected as atrazine and 17.7 μg kg⁻¹ was 2-hydroxy-atrazine. The detection of atrazine in the lowest layer was of almost four times higher mass than in the upper soil layer. These findings highlight the fact that atrazine is unexpectedly persistent in soil. The overall persistence of atrazine in the environment might represent a potential risk for successive groundwater contamination by leaching even after 22 years of environmental exposure.     

Observation and origin of organochlorine compounds and polycyclic aromatic hydrocarbons in the free troposphere over central Europe

On Zugspitze (2670 m a.s.l.), Alps, higher concentrations were observed during a winter than during a summer measurement campaign of PAHs, chlorobenzenes (43.6 vs. 2.0 pg m⁻³) and DDTs (3.7 vs. 1.2 pg m⁻³), while hexachlorocyclohexanes and PCBs were found at similar levels. The PCB, HCH and DDT levels are among the lowest ever reported from outside the Arctic. Mostly lower levels were found in samples collected in summer than in winter despite a significant boundary layer air influence, but no such influence on samples collected during the winter campaign. Boundary layer influence was quantified by Lagrangian particle dispersion model retroplume analyses. Photochemical lifetimes corresponding to k_OH < 1.5 × 10⁻¹² cm³ molec⁻¹ s⁻¹ are found for p,p′-DDT, k_OH < 0.75 × 10⁻¹² cm³ molec⁻¹ s⁻¹ for p,p′-DDE and k_OH < 1.0 × 10⁻¹² cm³ molec⁻¹ s⁻¹ for p,p′-DDD.     

Growing season methane budget of an Inner Mongolian steppe

We present a methane (CH₄) budget for the area of the Baiyinxile Livestock Farm, which comprises approximately 1/3 of the Xilin river catchment in central Inner Mongolia, P.R. China. The budget calculations comprise the contributions of natural sources and sinks as well as sources related to the main land-use in this region (non-nomadic pastoralism) during the growing season (May–September). We identified as important CH₄ sources floodplains (mean 1.55 ± 0.97 mg CH₄–C m^?2 h^?1) and domestic ruminants, which are mainly sheep in this area. Within the floodplain significant differences between investigated positions were detected, whereby only positions close-by the river or bayous emitted large amounts of CH₄ (mean up to 6.21 ± 1.83 mg CH₄–C m^?2 h^?1). Further CH₄ sources were sheepfolds (0.08–0.91 mg CH₄–C m^?2 h^?1) and pasture faeces (1.34 ± 0.22 mg CH₄–C g^?1 faeces dry weight), but they did not play a significant role for the CH₄ budget. In contrast, dung heaps were not a net source of CH₄ (0.0 ± 0.2 for an old and 0.0 ± 0.3 μg CH₄–C kg^?1 h^?1 for a new dung heap). Trace gas measurements along two landscape transects (volcano, hill slope) revealed expectedly a mean CH₄ uptake (volcano: 76.5 ± 4.3; hill: 28.3 ± 5.3 μg CH₄–C m^?2 h^?1), which is typical for the aerobic soils in this and other steppe ecosystems. The observed fluxes were rarely influenced by topography.The CH₄ emissions from the floodplain and the sheep were not compensated by the CH₄ oxidation of aerobic steppe soils and thus, this managed semi-arid grassland did not serve as a terrestrial sink, but as a source for this globally important greenhouse gas. The source strength amounted to 1.5–3.6 kg CH₄–C ha^?1 during the growing season, corresponding to 3.5–8.7 kg C ha^?1 yr^?1.     

Influence of a 1,800 MHz electromagnetic field on the EEG energy

The present study investigated the influence of electromagnetic fields (EMF), similar to that emitted by mobile phones, on brain activity. Ten women and ten men, matched for age and educational level, performed a short memory task (Wechsler test), with simultaneous Electroencephalogram (EEG) recordings at 15 scalp electrodes, both without (baseline) and with exposure to an 1,800 MHz signal. The EEG energy was found concentrated at the four basic EEG bands [α (8–13 Hz), β (14–30 Hz), δ (0–4 Hz), and θ (5–7 Hz)]. The analysis revealed that in the presence of EMF, the energy of the β band was significantly greater for females than for males at the majority of the electrodes. Since beta oscillation is associated with the shift of attention during the perception, these findings may indicate that the particular EMF (1,800 MHz signal) exerts an influence on this brain activity, which appears to be gender-related.