Environmental risk assessment of metals depends to a
great extent on modeling the fate and the mobility of metals
based on soil−liquid partitioning coefficients. A large
variability is observed among the reported values that could
be used to predict metal mobility and bioavailability. To
evaluate this, soil−liquid partitioning coefficients (K
d) for
many elements but especially for the metals cadmium, copper,
lead, nickel, and zinc were compiled from over 70 studies
of various origins collected from the literature. The
relationships between the reported values are explored
relative to variations in soil solution pH, soil organic matter
(SOM), and concentrations of total soil metal. The
results of multiple linear regressions show that K
d values
are best predicted using empirical linear regressions
with pH (with R
2 values of 0.29−0.58) or with pH and either
the log of SOM or the log of total metal and with resulting
R
2 values of 0.42−0.76. A semi-mechanistic model
based on the competitive adsorption of metal and H+
[dependent on solution pH, total metal content, and
log(SOM)] was a better tool to predict dissolved metal
concentrations (with R
2 values of 0.61−0.88), with the
exception of Pb (at 0.35).
BackgroundManganese is an essential nutrient, but in excess it can be a potent neurotoxicant. Despite the common occurrence of manganese in groundwater, the risks associated with this source of exposure are largely unknown.ObjectivesOur first aim was to assess the relations between exposure to manganese from drinking water and children’s intelligence quotient (IQ). Second, we examined the relations between manganese exposures from water consumption and from the diet with children’s hair manganese concentration.MethodsThis cross-sectional study included 362 children 6–13 years of age living in communities supplied by groundwater. Manganese concentration was measured in home tap water (MnW) and children’s hair (MnH). We estimated manganese intake from water ingestion and the diet using a food frequency questionnaire and assessed IQ with the Wechsler Abbreviated Scale of Intelligence.ResultsThe median MnW in children’s home tap water was 34 μg/L (range, 1–2,700 μg/L). MnH increased with manganese intake from water consumption, but not with dietary manganese intake. Higher MnW and MnH were significantly associated with lower IQ scores. A 10-fold increase in MnW was associated with a decrease of 2.4 IQ points (95% confidence interval: −3.9 to −0.9; p < 0.01), adjusting for maternal intelligence, family income, and other potential confounders. There was a 6.2-point difference in IQ between children in the lowest and highest MnW quintiles. MnW was more strongly associated with Performance IQ than Verbal IQ.ConclusionsThe findings of this cross-sectional study suggest that exposure to manganese at levels common in groundwater is associated with intellectual impairment in children.
We developed a semiempirical equation from metal complexation theory which relates the metal activity of soil solutions to the soil's pH, organic matter content (OM) and total metal content (MT). The equation has the general form:where pM is the negative logarithm (to base 10) of the metal activity, and a , b and c are constants. The equation successfully predicted free Cu2+ activity in soils with a wide range of properties, including soils previously treated with sewage sludge. The significant correlation of pCu to these measured soil properties in long-contaminated soils suggests that copper activity is controlled by adsorption on organic matter under steady state conditions. An attempt was made from separate published data to correlate total soluble Cu, Zn, Cd and Pb in soils to soil pH, organic matter content and total metal content. For Cu, the total Cu content of the soil was most highly correlated with total soluble Cu. Similarly, total soluble Zn and Cd were correlated with total metal content, but were more strongly related to soil pH than was soluble Cu. Smaller metal solubility in response to higher soil pH was most marked for Zn and Cd, metals that tend not to complex strongly with soluble organics. The organic matter content was often, but not always, a statistically significant variable in predicting metal solubility from soil properties. The solubility of Pb was less satisfactorily predicted from measured soil properties than solubility of the other metals. It seems that for Cu at least, solid organic matter limits free metal activity, whilst dissolved organic matter promotes metal solubility, in soils well-aged with respect to the metal pollutant. Although total metal content alone is not generally a good predictor of metal solubility or activity, it assumes great importance when comparing metal solubility in soils having similar pH and organic matter content.
The aerobic biotransformation over 180 days of two cationic quaternary ammonium compounds (QACs) with perfluoroalkyl chains was determined in soil microcosms, and biotransformation pathways were proposed. This is the first time that polyfluoroalkyl cationic surfactants used in aqueous film-forming foam (AFFF) formulations were studied for their environmental fate. The biotransformation of perfluorooctaneamido quaternary ammonium salt (PFOAAmS) was characterized by a DT50 value (time necessary to consume half of the initial mass) of 142 days and significant generation of perfluoroalkyl carboxylic acid (PFOA) at a yield of 30 mol % by day 180. The biotransformation of perfluorooctane sulfonamide quaternary ammonium salt (PFOSAmS) was very slow with unobservable change of the spiked mass; yet the generation of perfluorooctanesulfonate (PFOS) at a yield of 0.3 mol % confirmed the biotransformation of PFOSAmS. Three novel biotransformation intermediates were identified for PFOAAmS and three products including perfluorooctane sulfonamide (FOSA) for PFOSAmS through high-resolution mass spectrometry (MS) analysis and t-MS(2) fragmentation. The significantly slower PFOSAmS biotransformation is hypothesized to be due to its stronger sorption to soil owing to a longer perfluoroalkyl chain and a bulkier sulfonyl group, when compared to PFOAAmS. This study has demonstrated that despite overall high stability of QACs and their biocide nature, the ones with perfluoroalkyl chains can be substantially biotransformed into perfluoroalkyl acids in aerobic soil.
A review is presented of how one defines emerging contaminants and what can be included in that group of contaminants which is preferably termed “contaminants of emerging concern”. An historical perspective is given on the evolution of the issues surrounding emerging contaminants and how environmental scientists have tackled this issue. This begins with global lead contamination from the Romans two millennia ago, moves on to arsenic-based and DDT issues and more recently to pharmaceuticals, cyanotoxins, personal care products, nanoparticles, flame retardants, etc. Contaminants of emerging concern will remain a moving target as new chemical compounds are continuously being produced and science continuously improves its understanding of current and past contaminants.
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