Passive sampling and benchmarking to rank HOC levels in the aquatic environment

The identification and prioritisation of water bodies presenting elevated levels of anthropogenic chemicals is a key aspect of environmental monitoring programmes. Albeit this is challenging owing to geographical scales, choice of indicator aquatic species used for chemical monitoring, and inherent need for an understanding of contaminant fate and distribution in the environment. Here, we propose an innovative methodology for identifying and ranking water bodies according to their levels of hydrophobic organic contaminants (HOCs) in water. This is based on a unique passive sampling dataset acquired over a 10-year period with silicone rubber exposures in surface water bodies across Europe. We show with these data that, far from point sources of contamination, levels of hexachlorobenzene (HCB) and pentachlorobenzene (PeCB) in water approach equilibrium with atmospheric concentrations near the air/water surface. This results in a relatively constant ratio of their concentrations in the water phase. This, in turn, allows us to (i) identify sites of contamination with either of the two chemicals when the HCB/PeCB ratio deviates from theory and (ii) define benchmark levels of other HOCs in surface water against those of HCB and/or PeCB. For two polychlorinated biphenyls (congener 28 and 52) used as model chemicals, differences in contamination levels between the more contaminated and pristine sites are wider than differences in HCB and PeCB concentrations endorsing the benchmarking procedure

Systematic Review of Potential Health Risks Posed by Pharmaceutical, Occupational and Consumer Exposures to Metallic and Nanoscale Aluminum, Aluminum Oxides, Aluminum Hydroxide and Its Soluble Salts

Aluminum (Al) is a ubiquitous substance encountered both naturally (as the third most abundant element) and intentionally (used in water, foods, pharmaceuticals, and vaccines); it is also present in ambient and occupational airborne particulates. Existing data underscore the importance of Al physical and chemical forms in relation to its uptake, accumulation, and systemic bioavailability. The present review represents a systematic examination of the peer-reviewed literature on the adverse health effects of Al materials published since a previous critical evaluation compiled by Krewski et al. (2007). Challenges encountered in carrying out the present review reflected the experimental use of different physical and chemical Al forms, different routes of administration, and different target organs in relation to the magnitude, frequency, and duration of exposure. Wide variations in diet can result in Al intakes that are often higher than the World Health Organization provisional tolerable weekly intake (PTWI), which is based on studies with Al citrate. Comparing daily dietary Al exposures on the basis of “total Al”assumes that gastrointestinal bioavailability for all dietary Al forms is equivalent to that for Al citrate, an approach that requires validation. Current occupational exposure limits (OELs) for identical Al substances vary as much as 15-fold. The toxicity of different Al forms depends in large measure on their physical behavior and relative solubility in water. The toxicity of soluble Al forms depends upon the delivered dose of Al+ 3 to target tissues. Trivalent Al reacts with water to produce bidentate superoxide coordination spheres [Al(O2)(H2O4)+ 2 and Al(H2O)6 + 3] that after complexation with O2•−, generate Al superoxides [Al(O2•)](H2O5)]+ 2. Semireduced AlO2• radicals deplete mitochondrial Fe and promote generation of H2O2, O2 • − and OH•. Thus, it is the Al+ 3-induced formation of oxygen radicals that accounts for the oxidative damage that leads to intrinsic apoptosis. In contrast, the toxicity of the insoluble Al oxides depends primarily on their behavior as particulates. Aluminum has been held responsible for human morbidity and mortality, but there is no consistent and convincing evidence to associate the Al found in food and drinking water at the doses and chemical forms presently consumed by people living in North America and Western Europe with increased risk for Alzheimer\u27s disease (AD). Neither is there clear evidence to show use of Al-containing underarm antiperspirants or cosmetics increases the risk of AD or breast cancer. Metallic Al, its oxides, and common Al salts have not been shown to be either genotoxic or carcinogenic. Aluminum exposures during neonatal and pediatric parenteral nutrition (PN) can impair bone mineralization and delay neurological development. Adverse effects to vaccines with Al adjuvants have occurred; however, recent controlled trials found that the immunologic response to certain vaccines with Al adjuvants was no greater, and in some cases less than, that after identical vaccination without Al adjuvants. The scientific literature on the adverse health effects of Al is extensive. Health risk assessments for Al must take into account individual co-factors (e.g., age, renal function, diet, gastric pH). Conclusions from the current review point to the need for refinement of the PTWI, reduction of Al contamination in PN solutions, justification for routine addition of Al to vaccines, and harmonization of OELs for Al substances

Uptake and release kinetics of 22 polar organic chemicals in the Chemcatcher passive sampler

The Chemcatcher passive sampler, which uses Empore (TM) disks as sampling phase, is frequently used to monitor polar organic chemicals in river water and effluents. Uptake kinetics need to be quantified to calculate time-weighted average concentrations from Chemcatcher field deployments. Information on release kinetics is needed if performance reference compounds (PRCs) are used to quantify the influence of environmental conditions on the uptake. In a series of uptake and elimination experiments, we used Empore (TM) SDB disks (poly(styrenedivinylbenzene) copolymer modified with sulfonic acid groups) as a sampling phase and 22 compounds with a logK (ow) (octanol-water partitioning coefficient) range from -2.6 to 3.8. Uptake experiments were conducted in river water or tap water and lasted up to 25 days. Only 1 of 22 compounds (sulfamethoxazole) approached equilibrium in the uptake trials. Other compounds showed continuing non-linear uptake, even after 25 days. All compounds could be released from SDB disks, and desorption was proportionally higher in disks loaded for shorter periods. Desorption showed two-phase characteristics, and desorption was proportionally higher for passively sorbed compounds compared to actively loaded compounds (active loading was performed by pulling spiked river water over SDB disks using vacuum). We hypothesise that the two-phase kinetics and better retention of actively loaded compounds-and compounds loaded for a longer period-may be caused by slow diffusion of chemicals within the polymer. As sorption and desorption did not show isotropic kinetics, it is not possible to develop robust PRCs for adsorbent material like SDB disks

Evaluating organochlorine pesticide residues in the aquatic environment of the Lake Naivasha River basin using passive sampling techniques

Abstract Passive sampling techniques can improve the discovery of low concentrations by continuous collecting the contaminants, which usually go undetected with classic and once-off time-point grab sampling. The aim of this study was to evaluate organochlorine pesticide (OCP) residues in the aquatic environment of the Lake Naivasha river basin (Kenya) using passive sampling techniques. Silicone rubber sheet and Speedisk samplers were used to detect residues of αHCH, β-HCH, γ-HCH, δ-HCH, heptachlor, aldrin, heptachlor epoxide, pp-DDE, endrin, dieldrin, α-endosulfan, β-endosulfan, pp-DDD, endrin aldehyde, ppDDT, endosulfan sulfate, and methoxychlor in the Malewa River and Lake Naivasha. After solvent extraction from the sampling media, the residues were analyzed using gas chromatography electron capture detection (GC-ECD) for the OCPs and gas chromatographymass spectrometry (GC-MS) for the PCB reference compounds. Measuring the OCP residues using the silicone rubber samplers revealed the highest concentration of residues (∑OCPs of 81 (± 18.9 SD) μg/L) to be at the Lake site, being the ultimate accumulation environment for surficial hydrological, chemical, and sediment transport through the river basin. The total OCP residue sums changed to 71.5 (± 11.3 SD) μg/L for the Middle Malewa and 59 (± 12.5 SD) μg/L for the Upper Malewa River sampling sites. The concentration sums of OCPs detected using the Speedisk samplers at the Upper Malewa, Middle Malewa, and the Lake Naivasha sites were 28.2 (± 4.2 SD), 31.3 (± 1.8 SD), and 34.2 (± 6.4 SD) μg/L, respectively. An evaluation of the different pesticide compound variations identified at the three sites revealed that endosulfan sulfate, α-HCH, methoxychlor, and endrin aldehyde residues were still found at all sampling sites. However, the statistical analysis of one-way ANOVA for testing the differences of ∑OCPs between the sampling sites for both the silicone rubber sheet and Speedisk samplers showed that there was no significant difference from the Upper Malewa to the Lake site (P < 0.05). Finally, the finding of this study indicated that continued monitoring of pesticides residues in the catchment remains highly recommende

Air and seawater pollution and air–sea gas exchange of persistent toxic substances in the Aegean Sea: spatial trends of PAHs, PCBs, OCPs and PBDEs

Near-ground air (26 substances) and surface seawater (55 substances) concentrations of persistent toxic substances (PTS) were determined in July 2012 in a coordinated and coherent way around the Aegean Sea based on passive air (10 sites in 5 areas) and water (4 sites in 2 areas) sampling. The direction of air-sea exchange was determined for 18 PTS. Identical samplers were deployed at all sites and were analysed at one laboratory. hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs) as well as dichlorodiphenyltrichloroethane (DDT) and its degradation products are evenly distributed in the air of the whole region. Air concentrations of p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) and o,p'-DDT and seawater concentrations of p,p'-DDE and p,p'-DDD were elevated in Thermaikos Gulf, northwestern Aegean Sea. The polychlorinated biphenyl (PCB) congener pattern in air is identical throughout the region, while polybrominated diphenylether (PBDE)patterns are obviously dissimilar between Greece and Turkey. Various pollutants, polycyclic aromatic hydrocarbons (PAHs), PCBs, DDE, and penta- and hexachlorobenzene are found close to phase equilibrium or net-volatilisational (upward flux), similarly at a remote site (on Crete) and in the more polluted Thermaikos Gulf. The results suggest that effective passive air sampling volumes may not be representative across sites when PAHs significantly partitioning to the particulate phase are included