Approximately 40% of the volume of domestic sewage generated in the São Paulo State is untreated and released into water bodies, causing serious pollution problems that affect the water quality and especially the suspended sediments transported by rivers. Thus, this paper investigates the seasonal influence on the origin and fluxes of Cu, Co, Cr, Zn, Cd, Ni, Sc and particulate organic matter (POM) in sediments transported by a disturbed watershed in the São Paulo State, i.e. the Sorocaba River basin. POM was characterized using particulate organic carbon, particulate organic nitrogen, C:N ratio and δ13C and δ15N stable isotopic composition. Eight sample collections of fine suspended sediments (FSS) were carried out at the mouth of the Sorocaba River from July 2009 to May 2010. During the study period, the discharge rate followed the seasonal variation trend of the past 25 years. Zn was the most abundant trace element in the FSS, followed by Cr, Cu, Ni, Co, Sc and Cd. There was a higher concentration of trace elements during the dry season, except for Sc and Co, which did not vary seasonally. The POM showed the same trend, with higher concentrations during the dry season. The calculated enrichment factors and geoaccumulation index indicated that most of the trace elements are of geogenic origin, except for Zn, which showed significant anthropogenic contributions (55%). The elemental and isotopic analysis of C and N and C:N ratio indicated that the anthropogenic origin of POM found in the FSS is related mainly to domestic sewage (97%), while the significant correlation found between the concentrations of Zn and POM indicates that the main anthropogenic source of Zn is related to this domestic sewage. The FSS load transported during the study period was of 373,194 t y−1, of which 87% occurred during the rainy season.

Trace element profiling in the incrementally formed dentine of mammalian teeth can be applied to reconstruct temporal variation of incorporation of these elements into the tissue. Using an electron microprobe, this study analysed fluoride distribution in dentine of first and third mandibular molars of free-ranging eastern grey kangaroos inhabiting a high-fluoride area, to assess temporal variation in fluoride uptake of the animals. Fluoride content in the early-formed dentine of first molars was significantly lower than in the late-formed dentine of these teeth, and was also lower than in both, the early and the late-formed dentine of third molars. As early dentine formation in M1 takes place prior to weaning, this finding indicates a lower dentinal fluoride uptake during the pre-weaning compared to the post-weaning period. This is hypothetically attributed to the action of a partial barrier to fluoride transfer from blood to milk in lactating females and a low bioavailability of fluoride ingested together with milk. Another factor contributing to lower plasma fluoride levels in juveniles compared to adults is the rapid clearance of fluoride from blood plasma in the former due to their intense skeletal growth. The combined action of these mechanisms is considered to explain why in kangaroos from high-fluoride areas, the (early-formed) first molars are not affected by dental fluorosis while the (later-formed) third and fourth molars regularly exhibit marked to severe fluorotic lesions.

The second‒order rate constants (k) of hydroxyl radical (·OH) with polychlorinated biphenyls (PCBs) in the gas phase are of scientific and regulatory importance for assessing their global distribution and fate in the atmosphere. Due to the limited number of measured k values, there is a need to model the k values for unknown PCBs congeners. In the present study, we developed a quantitative structure–activity relationship (QSAR) model with quantum chemical descriptors using a sequential approach, including correlation analysis, principal component analysis, multi−linear regression, validation, and estimation of applicability domain. The result indicates that the single descriptor, polarizability (α), plays an important role in determining the reactivity with a global standardized function of lnk = −0.054 × α ‒ 19.49 at 298 K. In order to validate the QSAR predicted k values and expand the current k value database for PCBs congeners, an independent method, density functional theory (DFT), was employed to calculate the kinetics and thermodynamics of the gas‒phase ·OH oxidation of 2,4′,5-trichlorobiphenyl (PCB31), 2,2′,4,4′-tetrachlorobiphenyl (PCB47), 2,3,4,5,6-pentachlorobiphenyl (PCB116), 3,3′,4,4′,5,5′-hexachlorobiphenyl (PCB169), and 2,3,3′,4,5,5′,6-heptachlorobiphenyl (PCB192) at 298 K at B3LYP/6–311++G**//B3LYP/6–31 + G** level of theory. The QSAR predicted and DFT calculated k values for ·OH oxidation of these PCB congeners exhibit excellent agreement with the experimental k values, indicating the robustness and predictive power of the single–descriptor based QSAR model we developed.

Reconstructing the history of metal deposition in Singapore lake sediments contributes to understanding the anthropogenic and natural metal deposition in the data-sparse Southeast Asia. To this end, we present a sedimentary record of Pb, Pb isotopes and eleven other metals (Ag, As, Ba, Cd, Co, Cr, Cu, Ni, Tl, U and Zn) from a well-dated sediment core collected near the depocenter of MacRitchie Reservoir in central Singapore. Before the 1900s, the sedimentary Pb concentration was less than 2 mg/kg for both soil and sediment, with a corresponding 206Pb/207Pb of ∼1.20. The Pb concentration increased to 55 mg/kg in the 1990s, and correspondingly the 206Pb/207Pb decreased to less than 1.14. The 206Pb/207Pb in the core top sediment is concordant with the 206Pb/207Pb signal of aerosols in Singapore and other Southeast Asian cities, suggesting that Pb in the reservoir sediment was mainly from atmospheric deposition. Using the Pb concentration in the topmost layer of sediment, the estimated atmospheric Pb flux in Singapore today is ∼1.6 × 10−2 g/m2 yr. The concentrations of eleven other metals preserved in the sediment were also determined. A principal component analysis showed that most of the metals exhibit an increasing trend towards 1990s with a local concentration peak in the mid-20th century.

Effects of microplastic pollution on benthic organisms and ecosystem services provided by sedimentary habitats are largely unknown. An outdoor mesocosm experiment was done to realistically assess the effects of three different types of microplastic pollution (one biodegradable type; polylactic acid and two conventional types; polyethylene and polyvinylchloride) at increasing concentrations (0.02, 0.2 and 2% of wet sediment weight) on the health and biological activity of lugworms, Arenicola marina (Linnaeus, 1758), and on nitrogen cycling and primary productivity of the sediment they inhabit. After 31 days, A. marina produced less casts in sediments containing microplastics. Metabolic rates of A. marina increased, while microalgal biomass decreased at high concentrations, compared to sediments with low concentrations or without microplastics. Responses were strongest to polyvinylchloride, emphasising that different materials may have differential effects. Each material needs to be carefully evaluated in order to assess their risks as microplastic pollution. Overall, both conventional and biodegradable microplastics in sandy sediments can affect the health and behaviour of lugworms and directly or indirectly reduce primary productivity of these habitats.

In this study, polybrominated diphenyl ethers (PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) were analyzed in eleven freshwater fish species from Dianshan Lake, Shanghai, China. The highest concentrations of PBDEs and MeO-PBDEs were found in snakehead, with mean values of 38 ng g−1 lw and 4.2 ng g−1 lw, respectively. BDE-47 was the predominant congener of PBDEs, followed by BDE-154. Congener pattern variation of PBDEs was observed among different fish species, implying differences in biotransformation potential among fish. Yellow catfish showed highest concentrations of BDE-99, -153 and -183, suggesting that it is more resistant to debromination than any other fish analyzed in the present study. Trophic magnification factors were in the range of 1.35–1.81 for all the PBDE congeners, but not for 2′-MeO-BDE-68. Negative relationship was observed between PBDEs concentration and sample size (length and weight), indicating fish size dilution effect.

The most advanced epidemiological studies on health effects of air pollution assign exposure to individuals based on residential outdoor concentrations of air pollutants measured or estimated at the front-door. In order to assess to what extent this approach could cause misclassification, indoor measurements were carried out in unoccupied rooms at the front and back of a building which fronted onto a major urban road. Simultaneous measurements were also carried out at adjacent outdoor locations to the front and rear of the building. Two 15-day monitoring campaigns were conducted in the period June–December 2013 in a building located in the urban area of Bologna, Italy. Particulate matter metrics including PM2.5 mass and chemical composition, particle number concentration and size distribution were measured. Both outdoor and indoor concentrations at the front of the building substantially exceeded those at the rear. The highest front/back ratio was found for ultrafine particles with outdoor concentration at the front door 3.4 times higher than at the rear. A weak influence on front/back ratios was found for wind direction. Particle size distribution showed a substantial loss of particles within the sub-50 nm size range between the front and rear of the building and a further loss of this size range in the indoor data. The chemical speciation data showed relevant reductions for most constituents between the front and the rear, especially for traffic related elements such as Elemental Carbon, Iron, Manganese and Tin. The main conclusion of the study is that gradients in concentrations between the front and rear, both outside and inside the building, are relevant and comparable to those measured between buildings located in high and low traffic areas. These findings show high potential for misclassification in the epidemiological studies that assign exposure based on particle concentrations estimated or measured at subjects’ home addresses.

Trophic transfer of polybrominated diphenyl ethers (PBDEs) in aquatic ecosystems is an important criterion for assessing their environmental risk. This study analyzed 13 PBDEs in marine organisms collected from coastal area of Bohai Bay, China. The concentrations of total PBDEs (Σ13PBDEs) ranged from 12 ± 1.1 ng/g wet weight (ww) to 230 ± 54 ng/g ww depending on species. BDE-47 was the predominant compound, with a mean abundance of 20.21 ± 12.97% of total PBDEs. Stable isotopic ratios of carbon (δ13C) and nitrogen (δ15N) were analyzed to determine the food web structure and trophic level respectively. Trophic magnification factors (TMFs) of PBDEs were assessed as the slope of lipid equivalent concentrations regressed against trophic levels. Significant positive relationships were found for Σ13PBDEs and eight PBDE congeners (BDE-28, BDE-47, BDE-49, BDE-66, BDE-85, BDE-99, BDE-100 and BDE-154). Monte-Carlo simulations showed that the probabilities of TMF >1 were 100% for Σ13PBDEs, BDE-47, BDE-85, BDE-99 and BDE-100, 99% for DE-28, BDE-49, BDE-66 and BDE-154, 94% for BDE-153, and 35% for BDE-17.

Lead concentrations and isotopic compositions of contaminated urban soils and house dusts from Athens, Greece, have been determined to identify possible sources of Pb contamination and examine relationships between these two environmental media. Different soil particle sizes (<2000 μm, <200 μm, <100 μm, <70 μm, <32 μm) and chemical fractions (total, EDTA-extractable and acetic acid-extractable (HAc)) were analyzed for their Pb content and isotopic composition. Metal(loid)s (Pb, Zn, Cu, As, Ni, Cr, Mn, Fe) are significantly enriched in the finest fraction. The Pb isotopic compositions were similar for the different soil particle size fractions and different chemical extractions. The HAc extraction proved to be a useful procedure for tracing anthropogenic Pb in urban soil. The range of 206Pb/207Pb ratios (1.140–1.180) in Athens soil suggests that the Pb content represents an accumulated mixture of Pb deposited from past vehicular emissions and local natural sources. The contribution of anthropogenic Pb to total soil Pb ranged from 36% to 95%. The Pb isotopic composition of vacuum house dusts (206Pb/207Pb = 1.1.38–1.167) from Athens residents is mostly comparable to that of urban soil suggesting that exterior soil particles are transferred into homes. As a result, anthropogenic Pb in house dust from Athens urban environment principally originated from soil particles containing Pb from automobile emissions (former use of leaded gasoline).

Wind-driven sediment resuspension exerts significant effects on the P behavior in shallow lake ecosystems. In this study, a comprehensive dynamic phosphorus (P) model that integrates hydrodynamic, wind wave and sediment transport is proposed to assess the importance of internal P cycling due to sediment resuspension on water column P levels. The primary contribution of the model is detailed modeling and rigorous coupling of sediment and P dynamics. The proposed model is applied to predict the P behavior in the shallow Taihu Lake, which is the third largest lake in China, and quantitatively estimate the effects of wind waves and lake currents on P release and distribution. Both the prevailing southeast winds in summer and northwest winds in winter are applied for the simulation, and different wind speeds of 5 m/s and 10 m/s are also considered. Results show that sediment resuspension and the resulting P release have a dominant effect on P levels in Taihu Lake, and likely similar shallow lakes. Wind-driven waves at higher wind speeds significantly enhance sediment resuspension and suspended sediment concentration (SSC). Total P concentration in the water column is also increased but not in proportion to the SSC. The different lake circulations resulting from the different prevailing wind directions also affect the distribution of suspended sediment and P around the lake ultimately influencing where eutrophication is likely to occur. The proposed model demonstrates that internal cycling in the lake is a dominant factor in the lake P and must be considered when trying to manage water quality in this and similar lakes. The model is used to demonstrate the potential effectiveness of remediation of an area where historical releases have led to P accumulation on overall lake quality.