Photodissolution of submillimeter-sized microplastics and its dependences on temperature and light composition.

Photodissolution has the potential to efficiently remove microplastics from the surface ocean. Here, we examined the effects of temperature and incident sunlight composition on the photodissolution of submillimeter-sized microplastics of polypropylene (PP), polystyrene (PS), and thermoplastic polyurethane (TPU) in seawater. The photoproduction of dissolved organic carbon (DOC), chromophoric dissolved organic matter, and dissolved nitrogen (TPU only) was observed to increase exponentially within 7 days of full-spectrum irradiation. The temperature dependence of photodissolution increased with irradiation time for PP and PS but remained relatively constant for TPU. A 20 °C increase in temperature enhanced DOC photoproduction by 10 times for PP, three times for PS, and four times for TPU at 7-d irradiation, giving activation energies of 59.4-84.8 kJ mol-1. Photodissolution of all three polymers was exclusively driven by ultraviolet-B (UVB) radiation. PS-derived DOC was photomineralizable, while PP- and TPU-derived DOC appeared photo-resistant. Extrapolating the lab-based DOC photoproduction rates to warm surface oceans yields lifetimes of 6.5 years for PP, 3.6 years for PS, and 3.7 years for TPU. This study demonstrates that photodissolution of the tested microplastics is restricted to the thin UVB-penetrable surface ocean and that water temperature plays a critical role in controlling the photodissolution of these microplastics.

Distribution and environmental risk assessment of microplastics in continental shelf sediments in the southern East China Sea: A high-spatial-resolution survey.

We report a high-spatial-resolution study on the distributions, characteristics, and environmental risks of microplastics in surface sediments of the southern East China Sea. Microplastics were omnipresent in the sediments (concentration range: 53.3-246.7; mean: 138.4 particles/kg dry-weight sediment) and enriched in nearshore areas close to urban centers relative to lower offshore concentrations. The microplastics identified were dominated by polyethylene (41.2%) and polyethylene terephthalate (19.9%) in polymer type, fibers (45.8%) and fragments (40.3%) in shape, 0.1-0.5 mm (61.0%) in size, and black (52.0%) in color. The benthic environment experienced low to moderate microplastic pollution, with polyvinylchloride exhibiting the highest ecological risk index. The high-resolution sampling revealed highly diverse polymer types and strongly patchy distributions of microplastic abundance and pollution indices in sediments. Results from this study imply that complex physical, biological, and topographic interactions control the distribution of microplastics and the associated environmental risks in coastal sediments.

Bio- and photo-lability of dissolved organic matter in the Pearl River (Zhujiang) estuary.

We investigated the bio- and photo-lability of dissolved organic matter (DOM) from the head, mixing zone, and mouth of the Pearl River estuary. At all three sites, bio- and photo-refractory dissolved organic carbon (DOC) and biorefractory chromophoric DOM (CDOM) dominated over the corresponding bio- and photo-labile constituents, while photolabile CDOM dominated over photo-refractory CDOM. Relative to the mixing-zone and mouth waters, the headwater was enriched with bio- and photo-labile DOC and photolabile CDOM and depleted with biolabile CDOM. Biolabile DOC was richer than photolabile DOC in the headwater, while photolabile CDOM was richer than biolabile CDOM at all three sites. Pre-biotransformation inhibited, stimulated, or had little impact on DOM photodegradation, depending on site. Ultra-violet absorption coefficients are indicators of bio- and photo-refractory DOC. The relative proportions of transparent and chromophoric DOM control the turnover of biolabile DOC and the effect of pre-biotransformation on DOM photodegradation.

Photobleaching of chromophoric dissolved organic matter (CDOM) in the Yangtze River estuary: kinetics and effects of temperature, pH, and salinity.

The kinetics and temperature-, pH- and salinity-dependences of photobleaching of chromophoric dissolved organic matter (CDOM) in the Yangtze River estuary (YRE) were evaluated using laboratory solar-simulated irradiation and compared to those of Suwannee River humic substances (SRHSs). Nearly all CDOM in water at the head of the estuary (headwater herein) was photobleachable in both summer and winter, while significant fractions of CDOM (13-29%) were resistant to photobleaching in saltier waters. The photobleaching rate constant in the headwater was 25% higher in summer than that in winter. The absorbed photon-based photobleaching efficiency (PE) increased with temperature following the linear Arrhenius equation. For a 20 °C increase in temperature, PE increased by ∼45% in the headwater and by 70-81% in the saltier waters. PE for YRE samples exhibited minima at pH from 6 to 7 and increased with both lower and higher pH values, contrasting the consistent increase in PE with pH shown by SRHSs. No consistent effect of salinity on PE was observed for both SRHSs and YRE samples. Photobleaching increased the spectral slope coefficient between 275 nm and 295 nm in summer, consistent with the behavior of SRHSs, but decreased it in winter, implying a difference in the molecular composition of chromophores between the two seasons. Temperature, salinity, and pH modified the photoalteration of the spectral shape but their effects varied spatially and seasonally. This study demonstrates that CDOM quality, temperature, and pH should be incorporated into models involving quantification of photobleaching.

Carbon Monoxide Photoproduction from Particles and Solutes in the Delaware Estuary under Contrasting Hydrological Conditions.

Full-spectrum, ultraviolet (UV), and visible broadband apparent quantum yields (AQYs) for carbon monoxide (CO) photoproduction from chromophoric dissolved organic matter (CDOM) and particulate organic matter (POM) were determined in the Delaware Estuary in two hydrologically contrasting seasons in 2012: an unusually low flow in August and a storm-driven high flow in November. Average AQYs for CDOM and POM in November were 10 and 16 times the corresponding AQYs in August. Maximum AQYs in November occurred in a midestuary particle absorption maximum zone. Although POM AQYs were generally smaller than CDOM AQYs, the ratio of the former to the latter increased substantially from the UV to the visible. In both seasons, UV solar radiation was the primary driver for CO photoproduction from CDOM whereas visible light was the principal contributor to POM-based CO photoproduction. CDOM dominated CO photoproduction in the uppermost water layer while POM prevailed at deeper depths. On a depth-integrated basis, the Delaware Estuary shifted from a CDOM-dominated system in August to a POM-dominated system in November with respect to CO photoproduction. This study reveals that flood events may enhance photochemical cycling of terrigenous organic matter and switch the primary photochemical driver from CDOM to POM.

Distribution and spectral characteristics of chromophoric dissolved organic matter in a coastal bay in northern China.

The absorption spectra of chromophoric dissolved organic matter (CDOM), along with general physical, chemical and biological variables, were determined in the Bohai Bay, China, in the springs of 2011 and 2012. The absorption coefficient of CDOM at 350 nm (a350) in surface water ranged from 1.00 to 1.83 m⁻¹ (mean: 1.35 m⁻¹) in May 2011 and from 0.78 to 1.92 m⁻¹ (mean: 1.19 m⁻¹) in April 2012. Little surface-bottom difference was observed due to strong vertical mixing. The a350 was weakly anti-correlated to salinity but positively correlated to chlorophyll a (Chl-a) concentration. A shoulder over 260-290 nm, suggestive of biogenic molecules, superimposed the overall pattern of exponentially decreasing CDOM absorption with wavelength. The wavelength distribution of the absorption spectral slope manifested a pronounced peak at ca. 300 nm characteristic of algal-derived CDOM. All a250/a365 ratios exceeded 6, corresponding to CDOM molecular weights (Mw) of less than 1 kDa. Spectroscopically, CDOM in the Bohai Bay differed substantively from that in the Haihe River, the bay's dominant source of land runoff; photobleaching of the riverine CDOM enlarged the difference. Results point to marine biological production being the principal source of CDOM in the Bohai Bay during the sampling seasons. Relatively low runoff, fast dilution, and selective photodegradation are postulated to be among the overarching elements responsible for the lack of terrigenous CDOM signature in the bay water.

Carbon monoxide photoproduction: implications for photoreactivity of Arctic permafrost-derived soil dissolved organic matter.

Apparent quantum yields of carbon monoxide (CO) photoproduction (AQY(CO)) for permafrost-derived soil dissolved organic matter (SDOM) from the Yukon River Basin and Alaska coast were determined to examine the dependences of AQY(CO) on temperature, ionic strength, pH, and SDOM concentration. SDOM from different locations and soil depths all exhibited similar AQY(CO) spectra irrespective of soil age. AQY(CO) increased by 68% for a 20 °C warming, decreased by 25% from ionic strength 0 to 0.7 mol L(-1), and dropped by 25-38% from pH 4 to 8. These effects combined together could reduce AQY(CO) by up to 72% when SDOM transits from terrestrial environemnts to open-ocean conditions during summer in the Arctic. A Michaelis-Menten kinetics characterized the influence of SDOM dilution on AQY(CO) with a very low substrate half-saturation concentration. Generalized global-scale relationships between AQY(CO) and salinity and absorbance demostrate that the CO-based photoreactivity of ancient permaforst SDOM is comparable to that of modern riverine DOM and that the effects of the physicochemical variables revealed here alone could account for the seaward decline of AQY(CO) observed in diverse estuarine and coastal water bodies.

Investigations on the sorption of a toxaphene model congener, the B7-1450, on marine sediments.

Sorption is a natural process that takes place in sediments or soils and changes the mobility and availability of hydrophobic organic compounds, such as toxaphene pesticide in the environment. The sorption of the 2-exo,3-endo,5-exo,8,9,10,10-heptachlorobornane (B7-1450), used as a model compound of the toxaphene heptachlorobornane congeners found in sediments, was investigated for the first time through a series of batch sorption experiments. The losses of B7-1450 due to adsorption onto glass walls and to evaporation occurring during analytical treatment steps were corrected. The study showed that these specific losses ranged from 2% to 3.5% for the glass walls adsorption and can be as high as 15% for the evaporation treatment. The sorption coefficients, K(d) and K(oc), of B7-1450 could be overestimated by >30%, particularly for low-concentration samples, if the losses were not corrected. Loss correction equations were established, validated and applied to determine sorption coefficients for the B7-1450 congener. The K(oc) values for B7-1450 determined over a gradient of concentrations ranged from 3.5x10(4) to 6.5x10(4)mlg(-1), revealing a strong affinity of B7-1450 for marine sediments.

Photochemical alteration of the molecular weight of dissolved organic matter.

Molecular weight (MW) is a key control on the physical, chemical, and biological characteristics of dissolved organic mater (DOM). This study investigated the effect of photooxidation on the average MW of DOM by exposing DOM of diverse origins to simulated solar radiation at varying levels of dissolved oxygen and under different incident light wavelength regimes. During irradiation, high-molecular-weight fractions were destroyed and low-molecular-weight constituents were formed. The average MW decreased with irradiation time in all treatments in a manner that can be described by a quasi-exponential function, which suggests that solar radiation is incapable of completely mineralizing DOM even after prolonged exposure. Increasing the oxygen concentration accelerated the MW reduction while the removal of oxygen strongly suppressed this process. The fractional contributions from UV-B, UV-A, and visible radiations to full-spectrum photoinduced MW reduction varied considerably among the DOM samples examined, ranging from 19% to 60%, 17% to 36%, and 15% to 46%, respectively. The MW changes in time-series irradiations were inversely correlated with the ratio of the absorbance at 250 nm to that at 365 nm (i.e., the E(2)/E(3) quotient). Photoinduced MW reduction was accompanied by a decrease of polydispersity, which is indicative of a reduced DOM heterogeneity.

Effects of photodegradation of dissolved organic matter on the binding of benzo(a)pyrene.

Dissolved organic matter (DOM) in natural waters can bind various organic pollutants, and the affinity of this binding is strongly influenced by the chemical characteristics of the DOM and water pH. This study examined the effects of photochemically induced alteration of the DOM's chemical properties and water pH on the binding of benzo(a)pyrene (BaP). Time- and pH-series of solar-simulated irradiations were performed on a natural water sample and aqueous DOM solutions prepared from aquatic and soil humic substances. The binding affinity of BaP, expressed as a partition coefficient of a compound to DOM, decreased substantially after the DOM samples were irradiated over environmentally relevant radiation doses and pH ranges. The lowering of the pH due to the photoproduction of acidic products often partly offsets the reduction of the binding affinity caused by direct photoalteration of the DOM's chemical structure. The decrease of the binding affinity, after correction for the photoinduced pH change, was positively correlated with the decrease in the molecular weight and the aromaticity of the DOM in the course of irradiation. Increasing O(2) abundance accelerated the decrease of the binding affinity as a result of enhanced DOM photodegradation. Visible light played a more important role in reducing the molecular weight and aromaticity of the DOM than in reducing the content of dissolved organic carbon (DOC) via photoremineralization while the reverse was true for UV radiation, indicating that photochemical reduction of the binding affinity may occur in natural waters at depths greater than UV radiation can reach. A decrease of the affinity of DOM for binding BaP will increase the free dissolved fraction of BaP and thus its availability and toxicity to aquatic organisms. The results from this study may have similar implications for organic pollutants other than BaP.

Factors affecting the efficiency of carbon monoxide photoproduction in the St. Lawrence estuarine system (Canada).

This study examined the effects of water temperature and the origin (terrestrial vs marine) and light history of chromophoric dissolved organic matter (CDOM) on the apparent quantum yields of carbon monoxide (CO) photoproduction for water samples collected along a salinity gradient (salinity range: 0-33) in the St. Lawrence estuarine system (Canada). The solar insolation-weighted mean apparent quantum yield of CO (phico) decreased as much as fourfold with increasing salinity and showed a strong positive correlation with the dissolved organic carbon-specific absorption coefficient at 254 nm. This suggests that terrestrial CDOM is more efficient at photochemically producing CO than is marine algae-derived CDOM and that aromatic moieties are likely involved in this photoprocess. CDOM photobleaching, mainly at the very early stage, dramatically decreased phico (by up to 6.4 times) for low-salinity samples, but photobleaching had little effect on the most marine sample. For a 20 degree C increase in temperature, phico increased by approximately 70% for low-salinity samples and 30-40% for saline samples. This study demonstrates that water temperature, as well as the CDOM's origin and light history, strongly affect the efficiency of CO photoproduction. These factors should be taken into account in modeling the photochemical fluxes of CO and other related CDOM photoproducts on varying spatiotemporal scales.

Photooxidation and its effects on the carboxyl content of dissolved organic matter in two coastal rivers in the southeastern United States.

Photodecarboxylation (often stoichiometrically expressed as RCOOH + (1/2)O2 --> ROH + CO2) has long been postulated to be principally responsible for generating CO2 from photooxidation of dissolved organic matter (DOM). In this study, the quantitative relationships were investigated among O2 consumption, CO2 production, and variation of carboxyl content resulting from photooxidation of DOM in natural water samples obtained from the freshwater reaches of the Satilla River and Altamaha River in the southeastern United States. In terms of loss of dissolved organic carbon (DOC), loss of optical absorbance, and production of CO2, the rate of photooxidation of DOM was increased in the presence of Fe redox chemistry and with increasing O2 content. The ratio of photochemical O2 consumption to CO2 photoproduction ranged from approximately 0.8 to 2.5, depending on the O2 content, the extent of involvement of Fe, and probably the initial oxidation state of DOM as well. The absolute concentration of carboxyl groups ([-COOH]) on DOM only slightly decreased or increased over the course of irradiation, possibly depending on the stages of photooxidation, while the DOC-normalized carboxyl content substantially increased in the presence of Fe redox chemistry and sufficient O2. Both the initial [-COOH] and the apparent loss of this quantity over the course of irradiation was too small to account for the much larger production of CO2, suggesting that carboxyl groups were photochemically regenerated or that the major production pathway for CO2 did not involve photodecarboxylation. The results from this study can be chemically rationalized by a reaction scheme of (a) photodecarboxylation/ regeneration of carboxyl: CxHyOz(COOH)m + aO2 + (metals, hv) --> bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m-b(COOH)b or of (b) nondecarboxylation photooxidation: CxHyOz(COOH)m + aO2 + (metals, hv) --> bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m.