Emerged macrophytes to the rescue: Perfluoroalkyl acid removal from wastewater and spiked solutions

This study evaluated the potential for three emergent aquatic macrophytes to remove perfluoroalkyl acids (PFAAs) from contaminated waters in constructed wetland systems. Three plants (Iris pseudacorus L., Phragmites australis (Cav.) Trin. Ex Steud., and Typha latifolia L.) were exposed to an effluent from a tannery wastewater treatment plant (WWTP) that contained residual PFAAs, and to three spiked solutions with increasing concentrations of 11 perfluorocarboxylic acids (PFCAs) and three perfluorosulfonic acids (PFSAs) (500, 2500, and 5000 ng L-1, each). Thirty-six lightweight expanded clay aggregate-and vegetation-filled tanks (0.35 x 0.56 x 0.31 m) were exposed to the tested solutions at the Acque del Chiampo SpA WWTP in Arzignano (NE Italy). Throughout the experiment, PFAA concentrations and physicochemical water parameters were monitored via measures of the clay material, plastic tank inner surfaces, and below-and above-ground biomasses (after harvest). Vegetation growth was shown to be unaffected by increased PFAA levels in the spiked solutions. Alternatively, total biomass was significantly reduced when WWTP water was used, although we attribute this finding to the relatively high salinity that mainly restricted Typha and Iris development. The tested macrophytes were found to remove a significant PFAA mass from the contaminated waters (36% to ca. 80%, on average) when Phragmites was subjected to the highest PFAA concentrations. Such large accumulations were primarily associated with long C-chain PFAA stabilization in belowground biomass (26%, on average). Most PFAA trans locations were observed in Typha, which accumulated mostly short perfluorinated C-chain PFBA, PFPeA, and PFHxA in the aboveground biomass (16%, on average). Despite some growth limitations, Iris was still the most efficient macrophyte for translocating PFBS under WWTP

Uptake and translocation of perfluoroalkyl acids by hydroponically grown lettuce and spinach exposed to spiked solution and treated wastewaters

Perfluoroalkylated acids (PFAAs) are ubiquitous xenobiotic substances characterized by high persistence, bioaccumulation potential and toxicity, which have attracted global attention due to their widespread presence in both water and biota. In this study, the main objective was to assess PFAAs uptake and accumulation in lettuce (Lactuca sativa L.) and spinach (Spinacia oleracea L.) when fed with reclaimed wastewaters that are usually discharged onto a surface water body. Lettuce and spinach were grown in hydroponic solutions, exposed to two different municipal wastewater treatment plant (WWTP) effluents and compared with a spiked-PFAAs aqueous solution (nominal concentration of 500 ng L 121 for each perfluoroalkyl acid). Eleven perfluoroalkyl carboxylic acids and three perfluoroalkyl sulfonic acids were determined in the hydroponic solution, as well as quantified at the end of the growing cycle in crop roots and shoots. Water and dry plant biomass extracts were analyzed by liquid chromatography-electrospray ionization tandem spectrometry LC-MS/MS technique. The bioconcentration factor of roots (RCF), shoots (LCF), and the root-shoot translocation factor (TF) were quantified. In general, results showed that PFAAs in crop tissues increased at increasing PFAAs water values. Moreover some PFAAs concentrations (especially PFBA, PFBS, PFHxA, PFHpA, PFHxS) were different in both shoots and roots of lettuce and spinach, regardless of the type of water. The long C-chain PFAAs ( 659) were always below the detection threshold in WWTPs effluents. However, when PFAAs were detected, similar bioconcentration parameters were found between crops regardless the type of water. A sigmoidal RCF pattern was found as the perfluorinated chain length increased, plus a linear TF decrease. Comparing bioconcentration factor results with findings of previous studies, lettuce RCF value of PFCAs with perfluorinated chain length 64 9 and PFSAs was up to 10 times greater

Improved compaction of dried tannery wastewater sludge

We quantitatively studied the advantages of improving the compaction of a powder waste by several techniques, including its pelletization. The goal is increasing the mass storage capacity in a given storage volume, and reducing the permeability of air and moisture, that may trigger exothermic spontaneous reactions in organic waste, particularly as powders. The study is based on dried sludges from a wastewater treatment, mainly from tanneries, but the indications are valid and useful for any waste in the form of powder, suitable to pelletization. Measurements of bulk density have been carried out at the industrial and laboratory scale, using different packing procedures, amenable to industrial processes. Waste as powder, pellets and their mixtures have been considered. The bulk density of waste as powder increases from 0.64 t/m3 (simply poured) to 0.74 t/m3 (tapped) and finally to 0.82 t/m3 by a suitable, yet simple, packing procedure that we called dispersion filling, with a net gain of 28% in the compaction by simply modifying the collection procedure. Pelletization increases compaction by definition, but the packing of pellets is relatively coarse. Some increase in bulk density of pellets can be achieved by tapping; vibration and dispersion filling are not efficient with pellets. Mixtures of powder and pellets is the optimal packing policy. The best compaction result was achieved by controlled vibration of a 30/70 wt% mixture of powders and pellets, leading to a final bulk density of 1 t/m3, i.e. an improvement of compaction by more than 54% with respect to simply poured powders, but also larger than 35% compared to just pellets. That means increasing the mass storage capacity by a factor of 1.56. Interestingly, vibration can be the most or the least effective procedure to improve compaction of mixtures, depending on characteristics of vibration. The optimal packing (30/70 wt% powders/pellets) proved to effectively mitigate the onset of smouldering, leading to self-heating, according to standard tests, whereas the pure pelletization totally removes the self-heating hazard

Self-heating of dried industrial tannery wastewater sludge induced by pyrophoric iron sulfides formation

Similarly to many powders of solids, dried sludge originated from tannery wastewater may result in a self-heating process, under given circumstances. In most cases, it causes a moderate heating (reaching 70-90\ub0C), but larger, off-design residence times in the drier, in a suboxic atmosphere, extremely reactive solids can be produced. Tannery waste contains several chemicals that mostly end up in the wastewater treatment sludge. Unexpected and uncontrolled self heating could lead to a combustion and even to environmental problems. Elaborating on previous studies, with the addition of several analytical determinations, before and after the self-heating, we attempted to formulate a mechanism for the onset of heating. We demonstrated that the system Fe/S/O has been involved in the process. We proved that the formation of small quantities of pyrophoric iron sulfides is the key. They are converted to sulfated by reaction with water and oxygen with exothermic processes. The pyrite/pyrrhotite production depends on the sludge drying process. The oxidation of sulfides to oxides and sulfates through exothermic steps, reasonably catalyzed by metals in the sludge, occurs preferentially in a moist environment. The mechanism has been proved by reproducing in the laboratory prolonged heating under anoxic/suboxic atmosphere

New insights in the slow ligand exchange reaction between Cr(III)-EDTA and Fe(III), and direct analysis of free and complexed EDTA in tannery wastewaters by liquid chromatography - Tandem mass spectrometry

EDTA and soluble Cr(III) are usually both present in wastewaters coming from treatment plants handling tannery effluents. A well-established method to determine EDTA is based on the conversion of free and complexed EDTA into its Fe(III) complex. This procedure gives inconsistent data when Cr(III)-EDTA is present. This fact was here demonstrated by studying the kinetics of the exchange reaction between Fe(III) and Cr(III)-EDTA at 90 C and various pH values, from acidic to neutral. The reaction is very slow (several weeks); the slow kinetics of conversion of Cr(III)-EDTA to Fe(III)-EDTA is even more accentuated at room temperature and the low concentrations of reactants in wastewaters. The presence of EDTA complexes of Fe(III) and Cr(III) was demonstrated in industrial effluents and wastewaters by developing a selective method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS), which was able to detect free and complexed EDTA at concentration levels <1 mM. A systematic underestimation of the EDTA expressed as Fe(III) complex was demonstrated in samples containing Cr(III)-EDTA. Cr(III)- EDTA was identified for the first time as a component of wastewater samples at a concentration level of about 2 mM and turned out to be an inert species that significantly contributes to the final soluble Cr amount. This study gives new insights into the inertness of Cr(III) toward metal exchange equilibria of EDTA complexes, resolves a bias in the analysis of total EDTA in samples containing Cr(III)-EDTA, allowing the direct determination of free and complexed EDTA by LC-MS