Electrophilic cleavages in (CH3)3SnCH2M(CH3)3 (M = Sn, Ge, Si, C). 1. Product distribution

The extent to which Sn-CH2 and/or Sn-CH3 cleavage occurs in (CH3)3SnCH2M(CH3)3 (M = Sn, Ge, Si) in reactions with several electrophiles has been determined. With iodine and with bromine in various solvents both sites are attacked with Sn-CH2 cleavage favored for nonpolar solvents and for M = Sn. Protolysis leads to Sn-CH2 cleavage only, and this site appears to be activated by the (CH3)3M groups. On the other hand organometallic electrophiles exclusively attack the Sn-CH3 groups and the (CH3)3MCH2 groups are deactivating. With all reagents only the Sn-CH3 groups are reactive in (CH3)3SnCH2C(CH3)3. The complex mechanistic situation for halogenolysis can lead to variations in the relative reactivities of various sites during reaction and introduce serious errors into internal selectivity measurements

Estimating sludge loadings to land based on trace metal sorption in soil: effect of dissolved organo-metallic complexes

This paper describes the results of research examining the effect of dissolved organo-metallic complexes of copper (Cu) and zinc (Zn) from sewage sludge leachate on sorption by a humic-gley soil A-horizon, and the influence of such complexes on resultant sludge loading estimates. Sorption was described with Linear, Freundlich or Langmuir equations, and compared between a sample of sludge leachate (containing 97.4% of Cu and 63.2% of Zn as dissolved organo-metallic complexes) and a reference solution (which mimicked the leachate, except for a lack of dissolved organic material). This comparison revealed that dissolved organo-metallic complexes significantly depressed Cu and Zn sorption in the study soil. The isotherm equations were then used to estimate sludge-derived Cu and Zn loadings to soil in order to result in an "allowable" output concentration from the soil solution to the surrounding environment. These loadings, together with soil bulk density and "availability" of sludge Cu and Zn, were incorporated in a preliminary model to estimate sludge application rates which are acceptable in terms of off-site movement of these metals through leaching losses. In the absence of dissolved organo-metallic complexes (sorption from the reference solution), levels of Cu and Zn sorption in the study soil indicated a sludge application rate of approximately 3500 kg/ha. However, when Cu and Zn sorption from the sludge leachate with dissolved organo-metallic complexes was considered, calculated loading rates were reduced to approximately 690 kg-sludge/ha. This suggests that for sludge loading estimates based on soil sorption characteristics to be relevant to environmental protection, the sorption depressing effect of dissolved organo-metallic complexes should be quantitatively considered

Sludge-Derived Cu and Zn in a Humic-Gley Soil: Effect of Dissolved Metal-Organic Matter Complexes on Sorption and Partitioning

A sequential extraction scheme was combined with sorption isotherm analysis in order to investigate sorption of sewage sludge-derived Cu and Zn to the A-horizon of a humic-gley soil as a whole, and to the operationally defined exchangeable (1 M MgCl2), carbonate (1 M NaOAc), Fe/Mn oxide (0.04 M NH2OH.HCl), and organic (0.02 M HNO3+ 30% H2O2) soil fractions. Sorption parameters were compared for a sample of sludge leachate (with 97.4% of Cu and 63.2% of Zn present as dissolved metal-organic matter complexes, as calculated by geochemical modeling involving MINTEQA2 and verified using an ion exchange resin method) with that of a reference solution exhibiting the same chemical characteristics as the leachate, except for the presence of dissolved organic material. Dissolved metal-organic matter complexes were found to significantly (P < 0.05) depress sorption to the bulk soil and each fraction. The greatest depression of Cu and Zn sorption was observed for the exchangeable, carbonate, and Fe/Mn oxide fractions, while the organic fraction of the soil was the least affected. This reflects a greater affinity for the exchangeable, carbonate, and Fe/Mn oxide fractions by the free divalent metal (Cu2+, Zn2+), with sorption by these fractions attributed to cation exchange, chemisorption, and co-precipitation processes. The sorption characteristics of the organic fraction indicated that Cu and Zn sorption by soil organic matter mostly involved dissolved metal-organic matter complexes. This may be attributed to hydrophobic interactions between non-polar regions of the dissolved metal-organic matter complexes and solid-phase soil organic matter

Development and calibration of a passive sampler for N-nitrosodimethylamine (NDMA) in water

N-Nitrosamines such as N-nitrosodimethylamine (NDMA) are organic compounds of environmental concern in groundwater, wastewater and potable water due to their potent carcinogenicity in laboratory animal studies and probable human carcinogenicity. While passive sampling techniques have become a widely used tool for providing time-averaged estimates of trace pollutant concentration, for chemicals such as NDMA that have relatively high water solubility, the selection of a suitable sorbent is difficult. This work is a proof of principle study that investigated for the first time the use of coconut charcoal as a passive sampler sorbent. Apparent charcoal/water sorption coefficients for NDMA were >551 mL g(-1) at environmentally relevant aqueous concentrations of less than 1 mu g L(-1). Under the experimental conditions employed, a sampling rate of 0.45 Ld(-1) was determined and for an aqueous concentration of 1000 ng L(-1), it is predicted that the sampler remains in the linear uptake stage for approximately 4 d, while equilibrium attainment would require about 26 d. The presence of humic acid, used as a surrogate for DOC, enhanced NDMA sorption on the coconut charcoal

Characterisation and comparison of the uptake of ionizable and polar pesticides, pharmaceuticals and personal care products by POCIS and Chemcatchers

Growing concern about the environmental impact of ionizable and polar organic chemicals such as pesticides, pharmaceuticals and personal care products has lead to the inclusion of some in legislative and regulatory frameworks. It is expected that future monitoring requirements for these chemicals in aquatic environments will increase, along with the need for low cost monitoring and risk assessment strategies. In this study the uptake of 13 neutral and 6 ionizable pesticides, pharmaceuticals and personal care products by modified POCIS (with Strata™-X sorbent) and Chemcatchers™ (SDB-RPS or SDB-XC) was investigated under controlled conditions at pH = 6.5 for 26 days. The modified POCIS and Chemcatcher™ (SDB-RPS) samplers exhibited similar performance with the uptake of the majority of the 19 chemicals of interest categorised as linear over the 26 day deployment. Only a few ionized herbicides (picloram and dicamba) and triclosan showed negligible accumulation. Chemcatcher™ with SDB-XC sorbent performed relatively poorly with only carbamazepine having a linear accumulation profile, and 8 compounds showing no measurable accumulation. Differences in the uptake behavior of chemicals were not easily explained by their physico-chemical properties, strengthening the requirement for detailed calibration data. PES membranes accumulated significant amount of some compounds (i.e. triclosan and diuron), even after extended deployment (i.e. 26 days). At present there is no way to predict which compounds will demonstrate this behavior. Increasing membrane pore size from 0.2 to 0.45 µm for Chemcatcher™ (SBD-RPS) caused an average increase in Rs of 24%

Lifetime risk of knee and hip replacement following a GP diagnosis of osteoarthritis: a real-world cohort study

Objective: The aim of this study was to estimate lifetime risk of knee and hip replacement following a GP diagnosis of osteoarthritis and assess how this risk varies with patient characteristics. Methods: Routinely collected data from Catalonia, Spain, covering 2006 to 2015, were used. Study participants had a newly recorded GP diagnosis of knee or hip osteoarthritis. Parametric survival models were specified for risk of knee/hip replacement and death following diagnosis. Survival models were combined using a Markov model and lifetime risk estimated for the average patient profile. The effects of age at diagnosis, sex, comorbidities, socioeconomic status, body mass index (BMI), and smoking on risk were assessed. Results: 48,311 individuals diagnosed with knee osteoarthritis were included, of whom 2,561 underwent knee replacement. 15,105 individuals diagnosed with hip osteoarthritis were included, of whom 1,247 underwent hip replacement. The average participant's lifetime risk for knee replacement was 30% (95% CI: 25–36%) and for hip replacement was 14% (10–19%). Notable patient characteristics influencing lifetime risk were age at diagnosis for knee and hip replacement, sex for hip replacement, and BMI for knee replacement. BMI increasing from 25 to 35 was associated with lifetime risk of knee replacement increasing from 24% (20–28%) to 32% (26–37%) for otherwise average patients. Conclusion: Knee and hip replacement are not inevitable after an osteoarthritis diagnosis, with average lifetime risks of less than a third and a sixth, respectively. Patient characteristics, most notably BMI, influence lifetime risks.</p