Validation of an optimised microwave-assisted acid digestion method for trace and ultra-trace elements in indoor PM2.5 by ICP-MS analysis.

Three microwave-assisted digestion procedures, followed by analysis of digestates employing inductively coupled mass spectrometry (ICP-MS) were evaluated for use in the determination of elements at trace and ultra-trace levels in PM2.5 samples. Digestion procedure 1 used 2.5 mL HNO3 (65%) at 200 °C. Procedure 2, consisted of a two-stage digestion step at 200 °C with 2.5 mL HNO3 (65%) and 3 µL HF (48%) followed by 24 µL H3BO3 (5%). A 10-fold increase in the amounts of HF and H3BO3 was used for procedure 3. The addition of HF/H3BO3 was carried out to aid the dissolution of silicate matrices and refractory compounds. The digestions were carried out using PTFE ultra-trace inserts which increased the sample throughput threefold. The addition of small quantities of HF resulted in the effective solubilisation of Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Sr, Cd, Sb and Pb. The optimal method using HNO3/HF/H3BO3 digestion as in procedure 3 showed recovery efficiency greater than 70% for all elements. The validated method was applied to quantify the elemental content of indoor and outdoor PM2.5 (with samples <0.5 mg) at an urban background site in Malta.

Contamination of water resources of a small island state by fireworks-derived perchlorate: A case study from Malta.

We have previously reported on the ubiquitous presence of perchlorate in the deposited and airborne fine dusts of Malta and shown that the source of the chemical in the dusts of this small central Mediterranean island is fireworks. There are no local geologic or anthropogenic sources of perchlorate other than firework manufacture and display. The hypothesis was tested that ground-deposited perchlorate will be mobilized in runoff and would partly migrate to the water table and eventually also affect tap water, one third of which being derived from groundwater. Forty four percent of 36 groundwater samples contained perchlorate above detection limit with mean and median values of 1.09 and 1.1 µg L-1. Sixty-two percent of 16 runoff samples collected during storms contained perchlorate above detection limit with mean and maximum concentrations, respectively, of 50.8 and 129 µg L-1, values which are far too high to be explained by atmospheric inputs given that rainwater perchlorate levels are typically <3 µg L-1. Between 42 and 89% of the tap waters analyzed in three sampling campaigns contained perchlorate above detection limit and had mean concentrations ranging from 0.4 to 1.6 µg L-1 suggesting contamination levels similar to those reported from China but lower than levels reported from the USA. The phenomenon of contamination of the water resources of Malta by perchlorate is probably unique in that it results not from geologic or industrial inputs but from an intense and prolonged pyrotechnic activity that is deeply rooted in the popular culture of the islanders.

Perchlorate in dust fall and indoor dust in Malta: An effect of fireworks.

We report on the presence of perchlorate in the settleable dust of Malta, a small central Mediterranean island. Both dust fall collected directly as it precipitated from atmosphere over a period of one month and deposited indoor dust from domestic residences were studied. Perchlorate was determined by ion chromatography of water extracts of the collected dusts. Dust fall was collected from 43 towns during 2011 to 2013 and indoor dust was sampled from homes in the same localities. Perchlorate was detected in 108 of 153 samples of dust fall (71%) and in 28 of 37 indoor dust samples (76%). Detectable perchlorate in dust fall ranged from 0.52µgg(-1) to 561µgg(-1) with a median value of 6.2µgg(-1); in indoor dust, levels were from 0.79µgg(-1) to 53µgg(-1) with a median value of 7.8µgg(-1), the highest recorded anywhere to date. Statistical analysis suggested that there was no significant difference in perchlorate content of indoor dust and dust fall. Perchlorate levels in dust fall escalate during the summer in response to numerous religious feasts celebrated with fireworks and perchlorate persists at low µgg(-1) concentrations for several months beyond the summer festive period. In Malta, perchlorate derives exclusively from KClO4, imported for fireworks manufacture. Its residue in dust presents an exposure risk to the population, especially via ingestion by hand to mouth transfer. Our results suggest that wherever intensive burning of fireworks takes place, the environmental impact may be much longer lived than realised, mainly due to re-suspension and deposition of contaminated settled dust in the urban environment.

Environmental fate of triasulfuron in soils amended with municipal waste compost.

The amendment of soil with compost may significantly influence the mobility and persistence of pesticides and thus affect their environmental fate. Factors like adsorption, kinetics, and rate of degradation of pesticides could be altered in amended soils. The aim of this study was to determine the effects of the addition of compost made from source-separated municipal waste and green waste, on the fate of triasulfuron [(2-(2-chloroethoxy)-N-[[4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide], a sulfonylurea herbicide used in postemergence treatment of cereals. Two native soils with low organic matter content were used. A series of analyses was performed to evaluate the adsorption and degradation of the herbicide in soil and in solution after the addition of compost and compost-extracted organic fractions, namely humic acids (HA), fulvic acids (FA), and hydrophobic dissolved organic matter (HoDOM). Results have shown that the adsorption of triasulfuron to soil increases in the presence of compost, and that the HA and HoDOM fractions are mainly responsible for this increase. Hydrophobic dissolved organic matter applied to the soils underwent sorption reactions with the soils, and in the sorbed state, served to increase the adsorption capacity of the soil for triasulfuron. The rate of hydrolysis of triasulfuron in solution was significantly higher at acidic pH and the presence of organic matter fractions extracted from compost also slightly increased the rate of hydrolysis. The rate of degradation in amended and nonamended soils is explained by a two-stage degradation kinetics. During the initial phase, although triasulfuron degradation was rapid with a half-life of approximately 30 d, the presence of compost and HoDOM was found to slightly reduce the rate of degradation with respect to that in nonamended soil.