Optimized demineralization technique for the measurement of stable isotope ratios of nonexchangeable H in soil organic matter.

To make use of the isotope ratio of nonexchangeable hydrogen (δ(2)H(n (nonexchangeable))) of bulk soil organic matter (SOM), the mineral matrix (containing structural water of clay minerals) must be separated from SOM and samples need to be analyzed after H isotope equilibration. We present a novel technique for demineralization of soil samples with HF and dilute HCl and recovery of the SOM fraction solubilized in the HF demineralization solution via solid-phase extraction. Compared with existing techniques, organic C (C(org)) and organic N (N(org)) recovery of demineralized SOM concentrates was significantly increased (C(org) recovery using existing techniques vs new demineralization method: 58% vs 78%; N(org) recovery: 60% vs 78%). Chemicals used for the demineralization treatment did not affect δ(2)H(n) values as revealed by spiking with deuterated water. The new demineralization method minimized organic matter losses and thus artificial H isotope fractionation, opening up the opportunity to use δ(2)H(n) analyses of SOM as a new tool in paleoclimatology or geospatial forensics.

Polycyclic aromatic hydrocarbons (PAHs) and their polar derivatives (oxygenated PAHs, azaarenes) in soils along a climosequence in Argentina.

We evaluated the effects of soil properties and climate on concentrations of parent and oxygenated polycyclic aromatic compounds (PAHs and OPAHs) and azaarenes (AZAs) in topsoil and subsoil at 20 sites along a 2100-km north (N)-south (S) transect in Argentina. The concentrations of Σ29PAHs, Σ15OPAHs and Σ4AZAs ranged 2.4-38 ng g(-1), 0.05-124 ng g(-1) and not detected to 0.97 ng g(-1), respectively. With decreasing anthropogenic influence from N to S, low molecular weight PAHs increasingly dominated. The octanol-water partitioning coefficients correlated significantly with the subsoil to topsoil concentration ratios of most compounds suggesting leaching as the main transport process. Organic C concentrations correlated significantly with those of many compounds typical for atmosphere-soil partitioning. Lighter OPAHs were mainly detected in the S suggesting biological sources and heavier OPAHs in the N suggesting a closer association with parent-PAHs. Decreasing alkyl-naphthalene/naphthalene and 9,10-anthraquinone (9,10-ANQ)/anthracene ratios from N to S indicated that 9,10-ANQ might have originated from low-temperature combustion.