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Records of past climate can inform us on the natural range and mechanisms of climate change. In the arid Pacific southwestern United States (PSW), which includes southern California, there exist a variety of Holocene records that can be used to infer past winter conditions (moisture and/or temperature). Holocene records of summer climate, however, are rare from the PSW. In the future, climate changes due to anthropogenic forcing are expected to increase the severity of drought in the already water stressed PSW. Hot droughts are of considerable concern as summer temperatures rise. As a result, understanding how summer conditions changed in the past is critical to understanding future predictions under varied climate forcings. Here, we present a c. 10.9 kcal BP d18O.calcite/ record from Lake Elsinore, California, interpreted to reflect d18O.lake water/ values as controlled by over-water evaporation from summer-to-early fall. Our results reveal three millennial scale intervals: (1) the highly evaporative Early Holocene (10.55–6.65 kcal BP), (2) the less evaporative Mid-Holocene (6.65–2.65 kcal BP); and (3) the evaporative Late Holocene (2.65–0.55 kcal BP). These results are coupled with an inferred winter precipitation runoff (sand content) record from Kirby et al. (2010). Using these data together, we estimate the duration and severity of centennial-scale Holocene droughts and pluvials (e.g., high d18O.calcite/ values plus low sand content = drought and vice versa). Furthermore, the coupled d18O.calcite/ and sand data provide a generalized Holocene lake level history. The most severe, long-lasting droughts (i.e., maximum summer-to-early fall evaporation and minimum winter precipitation runoff) occur in the Early Holocene. Fewer, less severe, and shorter duration droughts occurred during the Mid-Holocene as pluvials became more common. Droughts return with less severity and duration in the Late Holocene. Notably, the Little Ice Age is characterized as the wettest period during the Late Holocene. 

High efficiency organic photovoltaic devices have relied on the development of new donor and acceptor materials to optimize opto-electronic properties, promote free carrier generation, and suppress recombination losses. With single junction efficiencies exceeding 15%, materials development must now target long-term stability. This work focuses on the photobleaching dynamics and degradation chemistries of a class of small molecule donors inspired by benzodithiophene terthiophene cores (BDT-3T) with rhodanine endcaps, which have demonstrated 9% efficiency in single junction devices and >11% in ternary cells. Density functional theory was used to design three additional molecules with similar synthetic pathways and opto-electronic properties by simply changing the electron accepting endcap to benzothiazoleacetonitrile, pyrazolone, or barbituric acid functional groups. This new class of semiconductors with equivalent redox properties enables systematic investigation into photobleaching dynamics under white light illumination in air. Degradation chemistries are assessed via unique spectroscopic signatures for the BDT-3T cores and the endcaps using photoelectron spectroscopies. We show that the pyrazolone undergoes significant degradation due to ring opening, resulting in complete bleaching of the chromophore. The barbituric and rhodanine endcap molecules have moderate stability, while the benzothiazoleacetonitrile group produces the most stable chromophore despite undergoing some oxidative degradation. Collectively, our results suggest the following: (i) degradation is not just dependent on redox properties; (ii) core group stability is not independent of the endcap choice; and (iii) future design of high efficiency materials must consider both photo and chemical stability of the molecule as a whole, not just individual donor or acceptor building blocks. 

A unique aqueous silica removal process using naturally occurring diatoms for water reuse and desalination is described. Several strains of brackish water diatoms have been isolated and tested. Among them Pseudostaurosira and Nitzschia species showed promise. Reverse osmosis (RO) concentrate samples from two full-scale advanced water purification facilities and one brackish groundwater RO plant in Southern California have been successfully treated by this process. This new photobiological process could remove aqueous silica, as well as phosphate, ammonia, nitrate, calcium, iron and manganese very effectively. Under non-optimized conditions, 95% of 78 mg·L-1 reactive silica in an RO concentrate sample could be removed within 72 hours. In most cases, addition of nutrients was not necessary because the RO concentrate typically contains sufficient concentrations of macronutrients derived from the source water (i.e., treated wastewater and brackish groundwater). Preliminary characterization of organics indicated that there was no major generation of dissolved organics, which could potentially foul membranes in the subsequent RO process. This new algal process has a strong potential for its application in desalination and water reuse in the United States and around the world.