Ranking REACH registered neutral, ionizable and ionic organic chemicals based on their aquatic persistency and mobility.

The contaminants that have the greatest chances of appearing in drinking water are those that are mobile enough in the aquatic environment to enter drinking water sources and persistent enough to survive treatment processes. Herein a screening procedure to rank neutral, ionizable and ionic organic compounds for being persistent and mobile organic compounds (PMOCs) is presented and applied to the list of industrial substances registered under the EU REACH legislation as of December 2014. This comprised 5155 identifiable, unique organic structures. The minimum cut-off criteria considered for PMOC classification herein are a freshwater half-life >40 days, which is consistent with the REACH definition of freshwater persistency, and a log Doc < 4.5 between pH 4-10 (where Doc is the organic carbon-water distribution coefficient). Experimental data were given the highest priority, followed by data from an array of available quantitative structure-activity relationships (QSARs), and as a third resort, an original Iterative Fragment Selection (IFS) QSAR. In total, 52% of the unique REACH structures made the minimum criteria to be considered a PMOC, and 21% achieved the highest PMOC ranking (half-life > 40 days, log Doc < 1.0 between pH 4-10). Only 9% of neutral substances received the highest PMOC ranking, compared to 30% of ionizable compounds and 44% of ionic compounds. Predicted hydrolysis products for all REACH parents (contributing 5043 additional structures) were found to have higher PMOC rankings than their parents, due to increased mobility but not persistence. The fewest experimental data available were for ionic compounds; therefore, their ranking is more uncertain than neutral and ionizable compounds. The most sensitive parameter for the PMOC ranking was freshwater persistency, which was also the parameter that QSARs performed the most poorly at predicting. Several prioritized drinking water contaminants in the EU and USA, and other contaminants of concern, were identified as PMOCs. This identification and ranking procedure for PMOCs can be part of a strategy to better identify contaminants that pose a threat to drinking water sources.

The distribution dynamics and desorption behaviour of mobile pharmaceuticals and caffeine to combined sewer sediments.

Pharmaceuticals are discharged to the environment from wastewater resource recovery facilities, sewer overflows, and illicit sewer connections. To understand the fate of pharmaceuticals, there is a need to better understand their sorption dynamics to suspended sediments (SS) and settled sediments (StS) in sewer systems. In this study, such sorption dynamics to both SS and StS were assessed using a batch equilibrium method under both static and dynamic conditions. Experiments were performed with natively occurring and artificially modified concentrations of sewer pharmaceuticals (acetaminophen, theophylline, carbamazepine, and a metabolite of carbamazepine) and caffeine. Differences in apparent distribution coefficients, Kd,app, between SS and StS were related to differences in their organic carbon (OC) content, and the practice of artificially modifying the concentration. Kd,app values of modified contaminant concentrations and high OC sediments were substantially higher. Pseudo-second order desorption rates for these mobile compounds were also quantified. Successive flushing events to simulate the addition of stormwater to sewer networks revealed that aqueous concentrations would not necessarily decrease, because the added water will rapidly return to equilibrium concentrations with the sediments. Sorption and desorption kinetics must be considered in addition to dilution, to avoid underestimating the influence of dilution on concentrations of pharmaceuticals discharged to the environment.

The presence and leachability of antimony in different wastes and waste handling facilities in Norway.

The environmental behaviour of antimony (Sb) is gathering attention due to its increasingly extensive use in various products, particularly in plastics. Because of this it may be expected that plastic waste is an emission source for Sb in the environment. This study presents a comprehensive field investigation of Sb concentrations in diverse types of waste from waste handling facilities in Norway. The wastes included waste electrical and electronic equipment (WEEE), glass, vehicle fluff, combustibles, bottom ash, fly ash and digested sludge. The highest solid Sb concentrations were found in WEEE and vehicle plastic (from 1238 to 1715 mg kg(-1)) and vehicle fluff (from 34 to 4565 mg kg(-1)). The type of acid used to digest the diverse solid waste materials was also tested. It was found that HNO3:HCl extraction gave substantially lower, non-quantitative yields compared to HNO3:HF. The highest water-leachable concentration for wastes when mixed with water at a 1 : 10 ratio were observed for plastic (from 0.6 to 2.0 mg kg(-1)) and bottom ash (from 0.4 to 0.8 mg kg(-1)). For all of the considered waste fractions, Sb(v) was the dominant species in the leachates, even though Sb(iii) as Sb2O3 is mainly used in plastics and other products, indicating rapid oxidation in water. This study also presents for the first time a comparison of Sb concentrations in leachate at waste handling facilities using both active grab samples and DGT passive samples. Grab samples target the total suspended Sb, whereas DGT targets the sum of free- and other chemically labile species. The grab sample concentrations (from 0.5 to 50 µg L(-1)) were lower than the predicted no-effect concentration (PNEC) of 113 µg L(-1). The DGT concentrations were substantially lower (from 0.05 to 9.93 µg L(-1)) than the grab samples, indicating much of the Sb is present in a non-available colloidal form. In addition, air samples were taken from the chimney and areas within combustible waste incinerators, as well as from the vent of WEEE sorting facility. The WEEE vent had the highest Sb concentration (from <100 to 2200 ng m(-3)), which were orders of magnitude higher than the air surrounding the combustible shredder (from 25 to 217 ng m(-3)), and the incinerator chimney (from <30 to 100 ng m(-3)). From these results, it seems evident that Sb from waste is not an environmental concern in Norway, and that Sb is mostly readily recovered from plastic and bottom ash.

Sorption and desorption of diverse contaminants of varying polarity in wastewater sludge with and without alum.

Sewage sludge sorption and desorption measurements were conducted for nine diverse contaminants of varying polarity: caffeine, sulfamethoxazole, carbamazepine, atrazine, estradiol, ethinylestradiol, diclofenac, and, for the first time desethylatrazine and norethindrone. Two types of sorption behaviour were observed. Compounds with a log octanol-water partition coefficient, log Kow, below 3 showed little or no sorption over 48 hours of shaking, while compounds with log Kow over 3 showed 30 to 90% sorption within the first few minutes. After 6 hours of shaking, mass loss through suspected biotransformation became evident for some compounds. At the pH range considered (5.7-6.7), diclofenac (pKa 4.0, log Kow 4.5) was the only compound in which pH dependent sorption could be quantified. The log sewage sludge-water distribution coefficients, log Kd, ranged from 0.2 to 2.9, and, as expected, increased with increasing log Kow of the compound and organic carbon (OC) content of the sewage sludge. A sewage sludge precipitated with alum had a substantially lower Kd values, as well as lower OC content, compared to alum-free sludge. Desorption was studied by sequentially replacing supernatant water. With each water replacement, log Kd values tended to either remain similar (following a linear isotherm) or in some cases increase (following a Freundlich-type isotherm). The length of time required to restore equilibrium increased with each rinsing step. A literature review of reported Kd values compared well with the alum-free sludge data, but not the alum-sludge data. Sewage sludge Kd across the literature appear more consistent with increasing Kow.

Comparison of polycyclic aromatic hydrocarbon uptake pathways and risk assessment of vegetables from waste-water irrigated areas in northern China.

Atmospheric deposition is the dominant pathway for PAH uptake by vegetables grown in peri-urban areas. Different polycyclic aromatic hydrocarbon (PAH) uptake pathways and the associated health risk were investigated in vegetable samples collected from the Beijing-Tianjin city cluster, China, where irrigation with waste or reclaimed water has been practised for many decades. Sampling comprised 23 diverse sites and the roots and shoots of six types of vegetables. Among the different edible vegetable parts, the highest PAH concentrations were found in radish roots and the lowest in cauliflower heads. Bioconcentration factors (BCFs) for individual PAHs showed a weakly decreasing trend with increasing log K(OW). To investigate whether the air-leaf or soil-root-shoot uptake dominates, the measured values were compared with estimations from a generic one-compartment model. The results and related observations are more consistent with an atmospheric uptake pathway than a soil-uptake pathway. The PAH isomeric ratios are consistent with pyrogenic sources (from combustion of fossil fuel and biomass). A health risk assessment on the consumption of the edible parts of vegetables revealed that all studied vegetables, except for 16% of Chinese cabbage samples, are safe for consumption. The results of this study indicate the potential health risk of consuming vegetables from waste-water irrigated areas of this city cluster and provide new insights regarding the transfer of PAHs in vegetables grown in this region.

Preparation, characterization, X-ray crystal structure, and energetics of cesium 5-cyano-1,2,3,4-tetrazolate: Cs[NCCNNNN].

Cesium 5-cyano-1,2,3,4-tetrazolate, Cs[NCCNNNN] (Cs1), was prepared in 100% yield by a 3 + 2 cycloaddition reaction of CsN3 and (CN)2 in SO2. Cs1 forms monoclinic crystals (a = 8.297(2) A, b = 11.040(3) A, c = 6.983(2) A, beta = 120.31(2) degrees, space group C2/c, Z = 4, R1 = 0.048, wR2 = 0.120 for 1217 independent reflections). Cs1 is best described as a three-dimensional array of cations and anions connected by weak Cs(+)-N delta- contacts. The cations and anions each form a diamond-type lattice (tetrahedral arrangement of ions) with the counterions lying in hexagonal channels running parallel to the c-axis. The anions in the channels form stacks with the CN groups pointing in opposite directions in adjacent layers. The calculated (RB3PW91/6-311 + G*) geometry of 1 is in agreement with the X-ray crystal structure, and the calculated vibrational spectrum is in good agreement with the observed FT-IR and FT-Raman spectra. The lattice enthalpies and heats of formation of M1 (M = Cs, K) as well as the enthalpy of formation from MN3(s) and (CN)2(g) were estimated. The 13C and 14N NMR spectra of Cs1 are also reported. The ionization potential (450.7 kJ mol) and electron affinity (427.4 kJ/mol) of 1 were calculated. Attempts to oxidize 1 with AsF5 led to the formation of Cs1.xAsF5 (x approximately 2). The 7 pi dianion [NCCNNNN].2- is calculated to be a stable entity in the gas phase, but Cs(2)1 is estimated to be unstable with respect to dissociation to 2 CsCN and 3/2 N2 (delta Hdiss = -132.4 kJ/mol). The preparation of the potassium salt of 1 and the corresponding thermodynamic quantities are reported.