A natural experiment indicated that a link between the presence and concentration of four elements, copper, lead, nickel, and zinc in the influent to two wastewater reclamation plants to the presence and concentrations of the same four elements in the tap water of residential properties. There were 36 populations of results that were assessed for the normality of their distribution, the difference in their median concentrations, the similarity in the ratios of their median concentrations, and the correlations of the concentrations. The results of this study suggest that brass corrosion is the major source of these four elements in the water reclamation plants influent and that there are two distinct populations of brass sources, those in the early stages of dezincification where the release of the non-copper elements is dominant and those in the later stages where the release of copper dominates and the type of brass that is corroding. Statistical analysis of residential tap waters and water reclamation plant influent showed that metals found in both came from brass corrosion.

Background, aim, and scope Benzotriazoles (BT) as 1H-benzotriazole (1H-BT), 5-methyl-1H-benzotriazole (5Me-BT), and 4-methyl-1H-benzotriazole (4Me-BT) are frequently used as corrosion inhibitors in dish washer detergents, aircraft de-icing/anti-icing fluids (ADAF), automotive antifreeze formulations, brake fluids, fluids for industrial cooling systems, metal-cutting fluids, and in solid cooling lubricants. Discharge of treated municipal waste water and controlled over-runs of combined waste water sewers are potential point sources for BT in rivers. The aim of this monitoring study was to yield an overview on exposure concentrations and loads of BT in the German rivers Main, Hengstbach, and Hegbach. Materials and methods Concentrations of 1H-BT, 5Me-BT, and 4Me-BT were determined in grab samples collected from different sampling points in the rivers Main, Hengstbach, and Hegbach at four different sampling times. Main and Hengstbach rivers were sampled close to Frankfurt International Airport. Both rivers receive domestic waste water effluents. BT were extracted from 2.5 L of river water by solid phase extraction using Bond Elut ppl cartridges (200 mg/3 mL). The extracts were analyzed by gas chromatography/mass spectrometry in full scan mode. Mass flows of BT were calculated by concentrations multiplied by mean daily river flow rates. Median concentrations and mass flows were compared for different rivers. Mass flows were also compared for selected sampling points at different sampling times. Results 1H-BT, 5Me-BT, and 4Me-BT were detected in Main and Hengstbach rivers. 1H-BT and 5Me-BT were also detected in Hegbach River. Concentrations ranged from 38 to 1,474 ng/L for 1H-BT, from 25 to 281 ng/L for 5Me-BT, and from 25 to 952 ng/L for 4Me-BT. Median concentrations of 1H-BT, 5Me-BT, and 4Me-BT were lower in Main than in Hengstbach River. Much higher median mass flows of all BT were calculated for Main than for Hengstbach River. At sampling points P9 (Main) and P5 (Hengstbach) concentrations of 4Me-BT and 5Me-BT increased from March 29, 2008 to May 1, 2008 to June 22, 2008 whereas daily mean river flow rate decreased simultaneously. However, concentration of 1H-BT in Main and Hengstbach River increased from March 29, 2008 to May 1, 2008 and decreased again on June 22, 2008. In the Main River, lowest and highest mass flows for all BT were calculated on June 22, 2008 and May 1, 2008, respectively. In the Hengstbach River lowest and highest mass flows for 1H-BT and 4Me-BT were also calculated on June 22, 2008 and May 1, 2008, respectively. However, mass flows of 5Me-BT in Hengstbach River were rather similar at all three sampling times. In all grab samples, 1H-BT was more abundant than 5Me-BT and 4Me-BT in Main and Hengstbach River, except on June 22, 2008. Ratios of 1H-BT/(5Me-BT + 4Me-BT) determined on March 15, 2008, March 29, 2008, and May 1, 2008 varied between 1.6 and 9.0 with a median value of 1.9 (n = 9) whereas on June 22, 2008 the ratios varied between 0.4 and 0.7 with a median value of 0.6 (n = 5). Discussion Due to the absence of waste water effluents in the Hegbach River, other input sources as controlled over-runs of combined waste water sewers and/or atmospheric deposition of BT must be regarded as possible input sources. Exfiltration of ground water containing BT to Hegbach River must be also regarded, especially when considering the high polarity of BT. Median concentrations of BT in Main River were much lower than in Hengstbach River due to dilution. However, median mass flows were higher in the Main River than in the Hengstbach River. Higher mass flows could be attributed to higher source strengths and/or numerous emissions sources in the Main River. Mass flows determined on June 22, 2008 in Main and Hengstbach rivers probably reflect emissions of BT only from dishwasher detergents since de-icing operations were unlikely at that time. Emissions of BT from dish washer detergents are rather constant without any seasonal variations. Assuming the absence of additional input sources and constant in-stream removal processes, mass flows calculated for all other sampling times must be nearly similar to mass flows for June 22, 2009 as it was only observed for 5Me-BT in Hengstbach River. The higher mass flows for 1H-BT and 4Me-BT in March and May in both rivers could be an indication for temporal variations of emission pattern and/or of in-stream removal processes. 1H-BT/(4Me-BT + 5Me-BT) ratios above one in March and May and below one in June could be also an indication for temporal variations of input and/or removal processes. Conclusions 1H-BT, 5Me-BT, and 4Me-BT used as corrosion inhibitors in many applications were detected in the rivers Main, Hengstbach, and Hegbach with relative high temporal and spatial concentration variations. Dilution is a dominant factor that influences exposure concentrations of BT in the studied rivers. We conclude that, especially in smaller rivers (as Hengstbach River), the hydrological situation has to be regarded when predicting exposure concentrations of BT. Characteristic emission strength and in-stream removal processes must be known to relate loads of BT in river water to different sources. The ratio of 1H-BT/(4Me-BT + 5Me-BT) could be possibly used for source apportionment. Recommendations and perspectives Time series analyses of BT in composite river water samples collected at two river sites of the Hengstbach/Schwarzbach catchment area, without any waste water effluents in between, are recommended to study in-stream removal of BT. In addition, exposure modeling is recommended of BT, regarding all input sources and in-stream removal processes to predict exposure concentrations of BT in rivers. In order to calibrate and validate the model, additional monitoring data are required.

Background, aim and scope The external surface of any building in urban polluted environment is unavoidably destined to be covered with layers that assume a grey to black colour and are generally called 'black crusts'. These, according to standard protocols and glossary, are deteriorated surface layers of stone material; they can have variable thickness, are hard and fragile and can detach spontaneously from the substrate, which, in general, is quite decayed. Plain visual examination may lead to consider 'black crusts' all similar, whilst only a careful diagnostic investigation can distinguish 'black crusts' and the consequences of their formation on stone substrates. In this paper, various black layers on marble are studied and compared and the morphological and compositional characteristics discussed according to the related mechanisms of formation. Differences between old (hundred years) and recent crusts (30 years) are investigated and pointed out. Materials and methods Samples of black crusts collected from the Milan Cathedral façade (Candoglia Marble) have been studied and compared with the careful and synergic employ of traditional techniques: optical (transmission and reflected VIS light) and electron microscopy, X-ray spectrometry and micro-Fourier transform infrared spectroscopy. Results Visual examination of loose fragments does not allow to point out outstanding differences amongst the various samples; black layers have similar main mineral components, gypsum and airborne particles, with different spatial distribution. The microscopic studies allowed to point out the porosity differences, the gypsum crystallisation habit, different amount of embedded particles, level and progress of marble decay. Discussion The observations lead to define three main types of black crusts: black crust deriving from marble sulphation, compact deposit and encrustation due to exogenic materials deposition. Black crusts show evidence of sulphation in progress, without a clear continuity solution between crust and marble; the lack of separation is particularly evident in 'recent' crust, where the sulphation process is more active. Black compact deposits show a higher porosity than black crusts because gypsum is not coming from the chemical corrosion of the substrate but from outside; actually, in the former case, the substrate is sound. Encrustations show a highly regular crystal organisation of gypsum (close packed tabular crystals) that cannot be traced back to casual atmospheric deposit or to corrosion of the substrate but rather to the crystallisation of a solution coming from an external source. Also in this case, the marble is sound; evidence of the effect of some protection treatment is pointed out. Conclusions In spite of the apparent similarity of the examined samples, analytical results have evidenced three main types of black crusts: black crust with decayed substrate, compact deposit and black encrustation showing a sound substrate underneath. Experimental evidence of calcite grains sulphation in progress, taking place according to a model recently proposed, has been observed. Sulphation process is prevented where particular conservation treatments had been applied in the past. Recommendations and perspectives New experimental studies can be focussed to understand the specific conditions (measurements of micro-climatic and thermodynamic parameters) and mechanisms for black crusts formation in situ. The problem of the kinetic of the sulphation process of marble, the assessment of black layers formation in the case of different carbonate stone materials and the study of acid attack in presence of surface protecting layers deserve further investigation.