A. Golchin et al., THE HETEROGENEOUS NATURE OF MICROBIAL PRODUCTS AS SHOWN BY SOLID-STATE C-13 CP MAS NMR-SPECTROSCOPY/, Biogeochemistry, 34(2), 1996, pp. 71-97
Homoionic Na-, Ca-, and Al-clays were prepared from the <2 mu m fracti
ons of Georgia kaolinite and Wyoming bentonite and mixed with sand to
give artificial soils with 5, and 25% clay. The artificial soils were
inoculated with microbes from a natural soil before incubation. Unlabe
lled and uniformly C-13-labelled (99.9% atom) glucose were incorporate
d into the artificial soils to study the effects of clay types, exchan
geable cations and clay contents on the mineralization of glucose-carb
on and glucose-derived organic materials. Chemical transformation of g
lucose-carbon upon incorporation into microbial products and metabolit
es, was followed using solid-state C-13 CP/MAS NMR spectroscopy. There
was a significant influence of exchangeable cations on the mineraliza
tion of glucose-carbon over a period of 33 days. At 25% clay content,
mineralization of glucose-carbon was highest in Ca-soils and lowest in
Al-soils. The influence of exchangeable cations on mineralization of
glucose-carbon was more pronounced in soils with bentonite clay than t
hose with kaolinite clay. Statistical analysis of data showed no overa
ll effect of clay type on mineralization of glucose-carbon. However, t
he interactions of clay type with clay content and clay type with clay
content and exchangeable cations were highly significant. At 25% clay
content, the mineralization of glucose-carbon was significantly lower
in Na- and Al-soils with Wyoming bentonite compared with Na- and Al-s
oils with Georgia kaolinite. For Ca-soils this difference was not sign
ificant. Due to the increased osmotic tension induced by the added glu
cose, mineralization of glucose-carbon was slower in soils with 5% cla
y than soils with 25% clay. Despite the differences in the chemical an
d physical characteristics of soils with Ca-, Na- and Al-clays, the ch
emical composition of organic materials synthesised in these soils wer
e similar in nature. Assuming CP/MAS is quantitative, incorporation of
uniformly C-13-labelled glucose (99.9% atom) in these soils resulted
in distribution of carbon in alkyl (24-25%), O-alkyl (56-63%), carbony
l (11-15%) and small amounts of aromatic and olefinic carbon (2-4%). H
owever, as decomposition proceeded, the chemistry of synthesised mater
ial showed some changes with time. In the Ca- and Na-soils, the propor
tions of alkyl and carbonyl carbon decreased and that of O-alkyl carbo
n increased with time of incubation. However, the opposite trend was f
ound for the Al-soil. Proton-spin relaxation editing (PSRE) subspectra
dearly showed heterogeneity within the microbial products. Subspectra
of the slowly-relaxing (long T-1(H)) domains were dominated by alkyl
carbon in long- and short-chain structures. The signals due to N-alkyl
(55 ppm) and carbonyl carbon were also strong in these subspectra. Th
ese subspectra were very similar to those obtained for microbial and f
ungal materials and were probably microbial tissues attached to clay s
urfaces by polysaccharide extracellular mucilage. Subspectra of fast-r
elaxing (short T-1(H)) domains comprised mostly O-alkyl and carbonyl c
arbon and were probably microbial metabolites released as neutral and
acidic sugars into the extracellular environment, and strongly sorbed
by clay surfaces.