Black crusts are recognized to have been, up to now, one of the major deterioration forms affecting the built heritage in urban areas. Their formation is demonstrated to occur mainly on carbonate building materials, whose interaction with an SO₂-loaded atmosphere leads to the transformation of calcium carbonate (calcite) into calcium sulfate dihydrate (gypsum) which, together with embedded carbonaceous particles, consequently forms the black crusts on the stone surface. An analytical study was carried out on black crust samples collected from limestone monumental buildings and churches belonging to the European built Heritage, i.e., the Corner Palace in Venice (Italy), the Cathedral of St. Rombouts in Mechelen (Belgium), and the Church of St. Eustache in Paris (France). For a complete characterization of the black crusts, an approach integrating different and complementary techniques was used, including laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), Fourier transform infrared spectroscopy, optical and scanning electron microscopy. In particular, the application of LA-ICP-MS permitted to obtain a complete geochemical characterization in terms of trace elements of the black crusts from the inner parts to the external layers contributing to the identification of the major combustion sources responsible for the deterioration over time of the monuments under study. In addition, the obtained results revealed a relation between the height of sampling and the concentration of heavy metals and proved that the crust composition can be a marker to evaluate the variation of the fuels used over time.

In the past three decades, the fast development of economy and urbanization has caused increasingly severe pollutions of urban water bodies in China. Consequently, eutrophication and deterioration of aquatic ecosystem, which is especially significant for aquatic vegetation, inevitably became a pervasive problem across the Yangtze River Basin. To rehabilitate the degraded urban water bodies, vegetation replanting is an important issue to improve water quality and to rehabilitate ecosystem. As a case study, a representative polluted urban river, Nanfeihe River, in Hefei City, Anhui Province, was chosen to be a rehabilitation target. In October 2009 and May 2010, 13 species of indigenous and prevalent macrophytes, including seven species emergent, one species floating leaved, and five species submersed macrophytes, were planted along the bank slopes and in the river. Through 1.5 years' replanting practice, the water quality and biodiversity of the river had been improved. The concentrations of total nitrogen (TN), total phosphorus (TP), and ammonia nitrogen (NH4 (+)-N) declined by 46.0, 39.5, and 60.4 %, respectively. The species of macrophytes increased from 14 to 60, and the biodiversity of phytoplankton rose significantly in the river (p < 0.05). The biomasses of zooplankton and benthos were also improved after the vegetation replanting. The study confirmed that vegetation replanting could alleviate the increasing water pollution and rehabilitate the degraded aquatic ecosystem. The case study would be an example for polluted urban waters restoration in the middle-downstream area of Yangtze River Base.

Several industries are using dyes as coloring agents. The effluents from these industries are increasingly becoming an environmental problem. The removal of dyes from aqueous solution has a great potential in the field of environmental engineering. This paper reviews the classification, characteristics, and problems of dyes in detail. Advantages and disadvantages of different methods used for dye removal are also analyzed. Among these methods, Fenton process-based advanced oxidation processes are an emerging prospect in the field of dye removal. Fenton processes have been classified and represented as “Fenton circle”. This paper analyzes the recent studies on Fenton processes. The studies include analyzing different configurations of reactors used for dye removal, its efficiency, and the effects of various operating parameters such as pH, catalyst concentration, H₂O₂ concentration, initial dye concentration, and temperature of Fenton processes. From the present study, it can be conclude that Fenton processes are very effective and environmentally friendly methods for dye removal.

Chromite ore processing residues (COPR) is the source of the Cr(VI) contamination in the environment. Pannonibacter phragmitetus BB was used to treat two different types of COPRs in this research. The water-soluble Cr(VI) of COPR A and B is 3,982.9 and 1,181.4 mg/kg, respectively. In the column biotreatment process, P. phragmitetus BB can reduce Cr(VI) in the leachate to an undetectable level at the flow rate of 1 and 2 ml/min. In the direct biotreatment process, Cr(VI) in the liquid supernatant of COPR A and B decreased from 265 and 200 mg/l to 145 and 40 mg/kg after 240 h of incubation. In one-step and two-step biotreatment processes, Cr(VI) in the liquid supernatant of both COPRs can be reduced to an undetectable level. The toxicity characteristic leaching procedure results indicate that the Cr(VI) concentration of treated COPR A (3.48 mg/l) is lower than the identification standards for hazardous wastes of China (5 mg/l) (GB 5085.6-2007). The information obtained in this study has significance for the application of P. phragmitetus BB to remediate COPR contamination.

The degradation of cyanobacterial blooms often causes hypoxia and elevated concentrations of ammonia, which can aggravate the adverse effects of blooms on aquatic organisms. However, it is not clear how one stressor would work in the presence of other coexistent stressors. We studied the toxic effects of elevated ammonia under hypoxia using a common yet important cladoceran species Daphnia similis isolated from heavily eutrophicated Lake Taihu. A 3 × 2 factorial experimental design was conducted with animals exposed to three un-ionized ammonia levels under two dissolved oxygen levels. Experiments lasted for 14 days and we recorded the life-history traits such as survival, molt, maturation, and fecundity. Results showed that hypoxia significantly decreased survival time and the number of molts of D. similis, whereas ammonia had no effect on them. Elevated ammonia significantly delayed development to maturity in tested animals and decreased their body sizes at maturity. Both ammonia and hypoxia were significantly detrimental to the number of broods, the number of offspring per female, and the number of total offspring per female, and significantly synergistic interactions were detected. Our data clearly demonstrate that elevated ammonia and hypoxia derived from cyanobacterial blooms synergistically affect the cladoceran D. similis.

Since the 1990s, the Lake Maggiore (Northern Italy) has been recognized as an aquatic environment contaminated by DDTs and other persistent organic pollutants, but to date just few studies were carried out to investigate the effects of pollution to aquatic organisms. The aim of this study was the application of a stepwise approach based on chemical data, a suite of biomarkers and the integration of their responses into a biomarker response index (BRI) to evaluate the site-specific quality assessment in different sampling stations of Lake Maggiore, one of the largest European lakes. We used as biological model the freshwater bivalve Zebra mussel (Dreissena polymorpha). Several hundred bivalve specimens were sampled on May 2011 from eight sampling sites located along the lake shoreline. We measured levels of DDTs, PCBs, HCHs, HCB, and PAHs accumulated in D. polymorpha soft tissues by GC/MSn, while the activities of catalase, superoxide dismutase, glutathione peroxidase, and glutathione S-transferase, as well as the lipid peroxidation and protein carbonyl content were evaluated in homogenates from native bivalves as oxidative stress indices. Moreover, DNA damage was investigated by the alkaline precipitation assay. Significant imbalances of enzymatic activity were found in mussels from most of the sampling sites, as well as notable increases of damage to macromolecules. Health status of mussels from Baveno was greatly affected by lake pollution, probably due to high levels of DDTs measured in this site, while a wide variability in biomarker responses was found in all the other stations. The application of a BRI allowed distinguishing impacts of pollution to bivalves, confirming mussels from Baveno as the most threatened and revealing that also the health status of bivalves from Suna, Brissago, Pallanza, and Laveno is affected. These evidences suggest the usefulness of a specific index to integrate all the biomarker endpoints in order to provide a correct environmental risk assessment.

The purpose of this work is to contribute to the understanding of the photochemical air pollution in central-southern of the Iberian Peninsula, analysing the behaviour and variability of oxidant levels (OX = O₃ + NO₂), measured in a polluted area with the highest concentration of heavy industry in central Spain. A detailed air pollution database was observed from two monitoring stations. The data period used was 2008 and 2009, around 210,000 data, selected for its pollution and meteorological statistics, which are very representative of the region. Data were collected every 15 min, however hourly values were used to analyse the seasonal and daily ozone, NO, NO₂ and OX cycles. The variation of OX concentrations with NO ₓ is investigated, for the first time, in the centre of the Iberian Peninsula. The concentration of OX was calculated using the sum of a NO ₓ -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO ₓ -dependent ‘local’ contribution. Monthly dependence of regional and local OX concentration was observed to determine when the maximum values may be expected. The variation of OX concentrations with levels of NO ₓ was also measured, in order to pinpoint the atmospheric sources of OX in the polluted areas. The ratios [NO₂]/[OX] and [NO₂]/[NO ₓ ] vs. [NO ₓ ] were analysed to find the fraction of OX in the form of NO₂, and the possible source of the local NO ₓ -dependent contribution, respectively. The progressive increase of the ratio [NO₂]/[OX] with [NO ₓ ] observed shows a greater proportion of OX in the form of NO₂ as the level of NO ₓ increases. The higher measured values in the ratio [NO₂]/[NO ₓ ] should not be attributed to NO ₓ emissions by vehicles; they could be explained by industrial emission, termolecular reactions or formaldehyde and HONO directly emitted by vehicles exhausts. We also estimate the rate of NO₂ photolysis, J NO₂ = 0.18–0.64 min⁻¹, a key atmospheric reaction that influence O₃ production and then the regional air quality. The first surface plot study of annual variation of the daily mean oxidant levels, obtained for this polluted area may be used to improve the atmospheric photochemical dynamic in this region of the Iberian Peninsula where there are undeniable air quality problems.

We evaluated 41 rural workers occupationally exposed to pesticides and 32 subjects as a control group, using the micronucleus (MN) and the comet assay. For the comet assay, we evaluated the peripheral blood, and for the MN, we sampled cells from the oral epithelium. Damage to DNA was measured by tail length, % DNA in tail (% tail), olive tail moment (OTM), and tail moment (TM). The exposed group presented an 8× increase in MN frequency, when compared to the control group (p <0.05). When we contrasted the MN frequencies between the individuals that use and do not use personal protective equipment, we found a mean of 7.5 MN (57 % variance) and 12.1 MN (130 % variance), respectively. The binucleated cells were 0.04 and 0.005, in the exposed and control groups, respectively, indicating 8× increase in the number of binucleated cells, when comparing the groups (p <0.05). In the comet assay, we demonstrated statistically significant differences in three parameters (% DNA, OTM, and TM) indicating that the rural workers presented high levels of genomic damages. Our results indicate that occupational exposure to pesticides could cause genome damage in somatic cells, representing a potential health risk to Brazilian rural workers that deal constantly with agrochemicals without adequate personal protection equipment.

Beef and dairy products may be important vectors of human exposure to perfluoroalkyl acids (PFAAs), but the understanding of how PFAAs are accumulated and transferred through agricultural food chains is very limited. Here, the bioaccumulation of PFAAs in dairy cows receiving naturally contaminated feed and drinking water was investigated by conducting a mass balance of PFAAs for a herd of dairy cows in a barn on a typical Swedish dairy farm. It was assumed that the cows were able to reach steady state with their dietary intake of PFAAs. Perfluorooctane sulfonic acid (PFOS) and perfluoroalkyl carboxylic acids (PFCAs) with 8 to 12 carbons were detected in cow tissue samples (liver, muscle, and blood) at concentrations up to 130 ng kg(-1). Mass balance calculations demonstrated an agreement between total intake and excretion within a factor of 1.5 and consumption of silage was identified as the dominant intake pathway for all PFAAs. Biomagnification factors (BMFs) were highly tissue and homologue specific. While BMFs of PFOS and PFCAs with 9 and 10 fluorinated carbons in liver ranged from 10 to 20, perfluorooctanoic acid (PFOA) was not biomagnified (BMF < 1) in any of the investigated tissues. Biotransfer factors (BTFs; defined as the concentration in tissue divided by the total daily intake) were calculated for muscle and milk. Log BTFs ranged from -1.95 to -1.15 day kg(-1) with the highest BTF observed for PFOS in muscle. Overall, the results of this study suggest that long-chain PFAAs have a relatively high potential for transfer to milk and beef from the diet of dairy cows. However, a low input of PFAAs to terrestrial systems via atmospheric deposition and low bioavailability of PFAAs in soil limits the amount of PFAAs that enter terrestrial agricultural food chains in background contaminated environments and makes this pathway less important than aquatic exposure pathways. The BTFs estimated here provide a useful tool for predicting human exposure to PFAAs via milk and beef under different contamination scenarios.

A long-term study was conducted to evaluate Piracicaba River water (So Paulo state, Brazil) using different methodologies and organisms. During 1 year (February 2011 to January 2012), water samples were collected monthly at six different locations and exposed under laboratory conditions to the microcrustaceans Ceriodaphnia dubia and Ceriodaphnia silvestrii for 7 days and to the fish Danio rerio for 4 days to evaluate effects on reproduction and on gill morphology, respectively. Physical-chemical parameters of the water were also measured. Physical-chemical characteristics demonstrated decreasing water quality from upstream to downstream of the river. Effects on the reproduction of C. dubia and C. silvestrii were observed in 3 months (February and March 2011 and January 2012) and occurred in samples collected close to industrialized cities like Americana and Piracicaba. Evaluation of the gills showed normal function of the organ during all months, except in February, September, and October for some locations.