The nature of Cu bonding to natural organic matter

Copper biogeochemistry is largely controlled by its bonding to natural organic matter (NOM) for reasons not well understood. Using XANES and EXAFS spectroscopy, along with supporting thermodynamic equilibrium calculations and structural and steric considerations, we show evidence at pH 4.5 and 5.5 for a five-membered Cu(malate)₂-like ring chelate at 100-300 ppm Cu concentration, and a six-membered Cu(malonate))_1-2-like ring chelate at higher concentration. A “structure fingerprint” is defined for the 5.0-7.0 Å⁻¹ EXAFS region which is indicative of the ring size and number (i.e., mono- vs. bis-chelate), and the distance and bonding of axial oxygens (O_ax) perpendicular to the chelate plane formed by the four equatorial oxygens (O_eq) at 1.94 Å. The stronger malate-type chelate is a C₄ dicarboxylate, and the weaker malonate-type chelate a C₃ dicarboxylate. The malate-type chelate owes its superior binding strength to an -OH for -H substitution on the α carbon, thus offering additional binding possibilities. The two new model structures are consistent with the majority of carboxyl groups being clustered and α-OH substitutions common in NOM, as shown by recent infrared and NMR studies. The high affinity of NOM for Cu(II) is explained by the abundance and geometrical fit of the two types of structures to the size of the equatorial plane of Cu(II). The weaker binding abilities of functionalized aromatic rings also is explained, as malate-type and malonate-type structures are present only on aliphatic chains. For example, salicylate is a monocarboxylate which forms an unfavorable six-membered chelate, because the OH substitution is in the β position. Similarly, phthalate is a dicarboxylate forming a highly strained seven-membered chelate.Five-membered Cu(II) chelates can be anchored by a thiol α-SH substituent instead of an alcohol α-OH, as in thio-carboxylic acids. This type of chelate is seldom present in NOM, but forms rapidly when Cu(II) is photoreduced to Cu(I) at room temperature under the X-ray beam. When the sample is wet, exposure to the beam can reduce Cu(II) to Cu(0). Chelates with an α-amino substituent were not detected, suggesting that malate-like α-OH dicarboxylates are stronger ligands than amino acids at acidic pH, in agreement with the strong electronegativity of the COOH clusters. However, aminocarboxylate Cu(II) chelates may form after saturation of the strongest sites or at circumneutral pH, and could be observed in NOM fractions enriched in proteinaceous material. Overall, our results support the following propositions:

(1)

The most stable Cu-NOM chelates at acidic pH are formed with closely-spaced carboxyl groups and hydroxyl donors in the α-position; oxalate-type ring chelates are not observed.

(2)

Cu(II) bonds the four equatorial oxygens to the heuristic distance of 1.94 ± 0.01 Å, compared to 1.97 Å in water. This shortening increases the ligand field strength, and hence the covalency of the Cu-O_eq bond and stability of the chelate.

(3)

The chelate is further stabilized by the bonding of axial oxygens with intra- or inter-molecular carboxyl groups.

(4)

Steric hindrances in NOM are the main reason for the absence of Cu-Cu interactions, which otherwise are common in carboxylate coordination complexes.

     

Testing the credibility of historical newspaper reporting of extreme climate and weather events

In recent years, newspaper research has been streamlined by digitisation and online hosting by PapersPast. This paper tests the reliability and credibility of reporting of extreme weather and climatic events through PapersPast to determine if newspaper research of past climate can be further streamlined. Searches were conducted through four early‐20th‐century Auckland newspapers, where counts of articles returned by key‐word searches for particular periods were compared against periods of known extremes. We find that blind searches have only limited potential in identifying extreme weather and climatic events and that they are no substitute for thorough analyses of documentary sources.     

Groundwater flux as a determinant of coastal-zone upland loss: a case study from the Pennsylvania coast of Lake Erie,USA

Climate change in the Great Lakes Basin of North America over the next several decades is projected to lead to significant changes to coastal environments. Groundwater-driven coastal bluff recession should increase in areas where groundwater forcing is important and lead to increased loss of coastal uplands. The latter is an issue in NW Pennsylvania because of coastal development pressures, and because the state ranks within the top five US states in grape production, most of which occurs within 5 km of the Lake Erie coastline. In 2007, viticulture contributed almost $2.4 billion to the state economy. An analysis of a 20-km stretch of coast shows that bluff retreat is pervasive and variable under current climatic conditions. Over a 9-year time frame, bluff change rates ranged from ?4.2 to +0.98 m/year. In general, higher retreat rates (?0.2 to ?0.65 m/year) occurred along the sandy central beach–ridge sector which lacks significant surface drainage. Lower retreat rates (?0.10 to ?0.25 m/year) occurred along coastal sectors where surface drainage networks are well developed. Conservative estimates of groundwater discharge at the bluff correlate strongly (r = 0.74, p < 0.001) with bluff retreat rate. Groundwater is inferred to be the principal driving mechanism for both bluff retreat and spatial variability in retreat rates on this coast. Other common factors that may spatially influence bluff retreat elsewhere (bluff height, land use, beach width) do not correlate strongly with retreat rate.     

Community-based responses to climate hazards: typology and global analysis

Climatic Change - The severity and frequency of climate change hazards are increasing around the world. Because the impacts are most acutely felt in local communities, it is critical to improve...